JP2003140370A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor containing a resin for a photoreceptor, which has sufficient mechanical strength, high solubility and solution stability even for a non-halogen solvent, excellent electric properties, particularly responding property. SOLUTION: The electrophotographic photoreceptor having at least a photosensitive layer on a conductive base body, is characterized in that the binder resin of the photosensitive layer has a polyarylate structure expressed by general formula (1), in which x and y are values representing the amounts of the respective units in the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member. More specifically, an electrophotographic photoreceptor containing a resin for an electrophotographic photoreceptor having excellent abrasion resistance, surface slipperiness, solubility when preparing a coating solution, storage stability of a coating solution, and good electrical responsiveness. It is about.

[0002]

2. Description of the Related Art In recent years, electrophotographic technology has been widely used and applied not only in the field of copying machines but also in the field of various printers because of its immediacy and high-quality images. Photoconductors, which are the core of electrophotographic technology, have been formed from conventional inorganic photoconductors such as selenium, arsenic-selenium alloy, cadmium sulfide, and zinc oxide as photoconductive materials. A photoreceptor using an organic photoconductive material, which has advantages such as easiness and easy production, has been developed.

As the organic photoreceptor, a so-called dispersion type photoreceptor in which a photoconductive fine powder is dispersed in a binder resin, and a laminated type photoreceptor in which a charge generation layer and a charge transfer layer are laminated are known. The laminated photoreceptor can be obtained by combining a highly efficient charge generating substance and a charge transfer substance to obtain a highly sensitive photoreceptor, a wide material selection range and a highly safe photoreceptor, and coating. Since it is highly productive and relatively advantageous in terms of cost, it is highly likely to become the mainstream of the photoreceptor and has been developed and put into practical use.

The electrophotographic photosensitive member is repeatedly used in an electrophotographic process, that is, in a cycle of charging, exposure, development, transfer, cleaning, charge elimination, and the like. Such deterioration includes, for example, strong oxidizing ozone and NOx generated from a corona charger commonly used as a charger, causing chemical damage to the photosensitive layer, and carrier (current) generated by image exposure. Is chemically and electrically deteriorated due to, for example, the flow of the compound in the photosensitive layer, the charge removal light, and the decomposition of the photosensitive layer composition due to external light.
Further, other deteriorations include mechanical deterioration such as abrasion or scratches on the surface of the photosensitive layer due to contact with cleaning blades, magnetic brushes or the like, contact with a developer or paper, and peeling of the film. In particular, such damages on the surface of the photosensitive layer tend to appear on the copy image and directly impair the image quality, which is a major factor limiting the life of the photosensitive member. That is, in order to develop a photoreceptor having a long life, it is essential to increase the electrical and chemical durability as well as the mechanical strength.

In general, in the case of a laminated type photoreceptor, it is the charge transfer layer that receives such a load. The charge transfer layer is usually composed of a binder resin and a charge transfer material, and it is the binder resin that substantially determines the strength.However, the doping amount of the charge transfer material is considerably large, so that sufficient mechanical strength has been reached. Not in. Also, with the increasing demand for high-speed printing,
Materials for higher speed electrophotographic processes are required. In this case, the photoreceptor must have high sensitivity and long life, and also have high responsiveness because the time from exposure to development is short. It is known that the responsivity of the photoreceptor is governed by the charge transfer layer, especially the charge transfer material, but also greatly depends on the binder resin.

[0006] Each layer constituting these electrophotographic photosensitive members is formed by dip coating, spray coating, nozzle coating, bar coating, roll coating, blade coating or the like on a support. In particular, as a method for forming the charge transfer layer, a known method such as coating as a coating solution obtained by dissolving a substance to be contained in the layer in a solvent is applied. In these current processes, a coating solution is prepared in advance and stored. Therefore, for the binder resin, the solvent used in the coating process,
Excellent solubility and stability of the coating solution after dissolution are also required.

Conventional binder resins for the charge transfer layer include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, polycarbonate, polyester, polysulfone, phenoxy, epoxy, and silicone resins. Thermoplastic resins and various thermosetting resins have been used. Among various binder resins, polycarbonate resins have relatively excellent performance, and various polycarbonate resins have been developed and put to practical use. For example, JP
JP-98-33232 discloses a bisphenol P-type polycarbonate, and JP-A-59-71057 discloses a bisphenol Z-type polycarbonate.
No. 9-184251 discloses a copolymer type polycarbonate of bisphenol P and bisphenol A,
JP-A-5-21478 discloses a polycarbonate copolymer having a bis (4-hydroxyphenyl) ketone type structure as a binder resin. However, conventional organic photoreceptors have drawbacks such as surface wear and surface damage due to practical loads such as development with toner, friction with paper, and friction with a cleaning member (blade). At present, the printing performance is limited in practical use.

On the other hand, Japanese Patent Application Laid-Open No. 56-135844 discloses a technique of an electrophotographic photoreceptor using a polyarylate resin commercially available under the trade name "U-Polymer" as a binder. It shows that the sensitivity is particularly excellent as compared with polycarbonate. JP-A-3-6567 discloses an electrophotographic photoreceptor characterized by containing a polyarylate copolymer having a structure using tetramethylbisphenol F and bisphenol A as a bisphenol component.

Japanese Patent Application Laid-Open No. 10-288845 discloses that the use of a polyarylate resin containing a bisphenol component having a specific structure as a binder resin improves the solution stability during the production of a photoreceptor. Japanese Unexamined Patent Publication No. 10-288846 discloses that an electrophotographic photosensitive member using a polyarylate resin having a specific kinematic viscosity range has excellent mechanical strength, particularly excellent abrasion resistance.

[0010]

However, when the currently used polycarbonate resin is used in an electrophotographic process, it is still insufficient in abrasion resistance, scratch resistance, responsiveness, adhesion to a substrate, and the like. Often. Further, in the commercially available polyarylate resin “U-Polymer”, although the abrasion resistance and the sensitivity were slightly improved, the stability of the coating solution was poor, and coating production was impossible. JP-A-3-6567
In the case of using a polyarylate copolymer having a structure using tetramethylbisphenol F and bisphenol A for the bisphenol component disclosed in Japanese Patent Application Publication, although mechanical properties are slightly improved, electrical properties, particularly, sensitivity and responsiveness are improved. However, sufficient performance has not been obtained.

Further, by using a polyarylate resin having a specific structure disclosed in JP-A-10-288845 and JP-A-10-288846, the solubility /
Although the solution stability and the mechanical strength are improved, the demand for high-speed printing has recently been increased, and the electrical characteristics, particularly the responsiveness, have been insufficient. Therefore, at present, there is a demand for a binder resin which is easily soluble in a mechanical strength and a non-halogen solvent, has excellent solution stability, and has excellent responsiveness.

Further, Japanese Patent Application Laid-Open No. 57-73021 discloses a polyarylate having a specific structure having excellent heat resistance. However, this publication does not disclose the concept of adapting the polyarylate having the specific structure to an electrophotographic photosensitive member, or the required mechanical properties and electrical properties.

[0013]

The inventors of the present invention have studied the binder resin used in the photosensitive layer in detail, and have found that the use of a polyarylate resin having a specific structure as a binder resin has sufficient mechanical properties. However, they have found that they have high solubility and excellent solution stability even in non-halogen solvents, and are excellent in electrical characteristics, particularly in responsiveness.

That is, a first gist of the present invention is to provide an electrophotographic photosensitive member having at least a photosensitive layer on a conductive substrate, wherein the binder resin of the photosensitive layer is a polyarylate represented by the following general formula (1). An electrophotographic photosensitive member having a structure.

[0015]

Embedded image (The structure represented by the following general formula (2) in the general formula (1) is at least one selected from the structures represented by the following general formula (3).)

[0016]

Embedded image

[0017]

Embedded image (A and b in the general formula (3) are 0 ≦ a ≦ 1, 0 ≦ b
≦ 1 and a + b = 1. (The structure represented by the following general formula (4) in the general formula (1) is at least one kind selected from the structures represented by the following general formulas (5), (6) and (7). is there.)

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image (In the general formula (1), x and y are values indicating the amount in the resin.) (Also, the general formula (5) in all bisphenol components constituting the polyarylate structure represented by the general formula (1) The structural component represented by) does not exceed 45%.)

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. <Resin for Electrophotographic Photoreceptor> The electrophotographic photoreceptor of the present invention comprises:
The binder resin of the photosensitive layer has a polyarylate structure represented by the general formula (1).

Next, specific examples of the polyarylate structure represented by the general formula (1) will be shown, but the present invention is not limited to these specific examples. The structure represented by the general formula (2) in the general formula (1) is a residue derived from an aromatic dicarboxylic acid component used in producing the polyarylate resin used in the present invention.

As the aromatic dicarboxylic acid component, a mixture having a structure represented by the general formula (3) is used. Specifically, terephthalic acid derivatives and isophthalic acid derivatives,
For example, terephthalic acid chloride and isophthalic acid chloride are used. In the general formula (3), a and b are 0 ≦ a
/ (A + b) ≦ 1, but preferably 0.01 ≦ a / (a + b) ≦ 1, more preferably 0.5
≦ a / (a + b) ≦ 1, particularly preferably a / (a
+ B) = 1. If the value of a / (a + b) is small, it is not preferable because the electrical characteristics and the mechanical characteristics of the photoconductor are reduced.

In the general formula (1), x and y are 0.1 ≦ x /
It is a value satisfying (x + y) ≦ 0.9, preferably in the range of 0.2 ≦ x / (x + y) ≦ 0.8, particularly preferably in the range of 0.3 ≦ x / (x + y) ≦ 0.7. This is a satisfactory value. If the value of x / (x + y) is larger than this range, it is not preferable because the electrical characteristics and the mechanical characteristics of the photoconductor are deteriorated. On the other hand, if it is smaller than this range, the solubility / solution stability in a non-halogen solvent or the like deteriorates, which is not preferable.

The structure represented by the general formula (4) in the general formula (1) includes at least two types selected from the structures represented by the general formulas (5), (6) and (7). It is a thing. In addition, among these, the general formula (5) is preferably used.
And at least one selected from the structures represented by the general formulas (6) and (7).

Specific examples of the bisphenol component having these structures include bis (4-hydroxyphenyl) methane [p, p'-BPF] and (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o, p '-BPF] and bis (2-
Hydroxyphenyl) methane [o, o'-BPF].
In other words, the preferred structure has a polyarylate structure represented by the general formula (9), and has a general formula (10)
And at least one of the structures represented by (11).

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image (In the general formula, m, n, o and p are values indicating the amount in the resin, and 0 <n / (m + n + o + p) ≦ 0.45.) The general formulas (9), (10) and (10) A preferable ratio of the polyarylate structure represented by 11) is m,
Each of n, o and p is 0.2 ≦ m / (m + n + o + p) ≦ 0.8 0.01 ≦ n / (m + n + o + p) <0.40 ≦ o / (m + n + o + p) <0.30 ≦ p / (m + n + o + p) ) <0.3 and 0.7 ≦ (m + n) / (m + n + o + p) ≦
0.95 0.05 ≦ (o + p) / (m + n + o + p) ≦ 0.3, particularly preferably 0.3 ≦ m / (m + n + o + p) ≦ 0.7 0.1 ≦ n / (m + n + o + p) <0.40 ≦ o / (m + n + o + p) <0.20 ≦ p / (m + n + o + p) <0.1 and 0.8 ≦ (m + n) / (m + n + o + p) ≦
0.9 0.1 ≦ (o + p) / (m + n + o + p) ≦ 0.2.

If the value of m / (m + n + o + p) is larger than this range, it is not preferable because the electrical characteristics and the mechanical characteristics of the photosensitive member are deteriorated. Also,
If it is smaller than this range, the solubility / solution stability in a non-halogen solvent or the like deteriorates, which is not preferable. n / (m
If the value of (+ n + o + p) is larger than this range, the solubility / solution stability in a non-halogen solvent or the like becomes poor, which is not preferable. On the other hand, if it is smaller than this range, the mechanical properties of the photoreceptor are undesirably deteriorated.

If the value of o / (m + n + o + p) is larger than this range, the reactivity during polymerization decreases, and it is difficult to control the molecular weight or to obtain a high molecular weight compound, which is not preferable. If the value of p / (m + n + o + p) is larger than this range, the mechanical properties of the photoreceptor, particularly the abrasion resistance, are undesirably reduced. Also, (m + n) / (m + n + o +
When p) and (o + p) / (m + n + o + p) are in the above ranges, the balance between the respective performances and characteristics is good, and it is preferable. If the ratio is out of this range, the balance is lost and the above-mentioned characteristics and performance are deteriorated.

<Method for Producing Resin for Electrophotographic Photoreceptor> As a method for producing the resin for an electrophotographic photoreceptor of the present invention, a known polymerization method can be used. For example, an interfacial polymerization method, a melt polymerization method, a solution polymerization method and the like can be mentioned. For example, in the case of production by an interfacial polymerization method, a solution in which a bisphenol component is dissolved in an aqueous alkaline solution is mixed with a solution of a halogenated hydrocarbon in which an aromatic dicarboxylic acid chloride component is dissolved. In this case, a quaternary ammonium salt or a quaternary phosphonium salt can be used as a catalyst.
The polymerization temperature is preferably in the range of 0 to 40 ° C, and the polymerization time is preferably in the range of 2 to 12 hours from the viewpoint of productivity. After polymerization,
The desired resin can be obtained by separating the aqueous phase and the organic phase, and washing and collecting the polymer dissolved in the organic phase by a known method.

The alkaline component used here is:
Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of the alkali used is as follows: 1. The amount of the phenolic hydroxyl group contained in the reaction system.
A range of 01 to 3 equivalents is preferred. Further, as the halogenated hydrocarbon used herein, dichloromethane,
Chloroform, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dichlorobenzene and the like can be mentioned.

The quaternary ammonium salt or quaternary phosphonium salt used as a catalyst includes salts of tertiary alkylamines such as tributylamine and trioctylamine with hydrochloric acid, bromate and iodate, benzyltriethylammonium chloride, benzyltrimethyl Ammonium chloride, benzyltributylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylphosphonium bromide, triethyloctadecylphosphonium bromide, N-laurylpyridinium chloride, laurylpicolinium chloride, etc. No.

In the polymerization, phenol, o, m, p-cresol, o, m, p-ethylphenol, o, m, p-propylphenol,
alkylphenols such as o, m, p-tert-butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol and 2,6-dimethylphenol derivatives; monofunctional phenols such as o, m, p-phenylphenol; Monofunctional acid halides such as chloride, butyric acid chloride, octylic acid chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride and substituted products thereof may be present. Of these molecular weight regulators,
A 6-dimethylphenol derivative is preferred because of its high molecular weight controllability.

Specific examples of the 2,6-dimethylphenol derivative include 2,6-dimethylphenol, 2,3,6
-Trimethylphenol, 2,4,6-trimethylphenol, 2,3,4,6-tetramethylphenol,
2,6-dimethyl-4-t-butylphenol, 2,6
-Dimethyl-4-nonylphenol, 2,6-dimethyl-4-acetylphenol, α-tocopherol and the like are fried. Among these, 2,3,6-trimethylphenol is preferred in view of the solution stability of the produced polymer.

In the polyarylate resin comprising a repeating unit having the structure represented by the general formula (1), groups present at the molecular chain terminals, such as the above-mentioned molecular weight modifier, are not included in the repeating unit. General formula (1) of the present invention
Has a viscosity average molecular weight of 10,000 or more and 300,000 or less, preferably 15,000 or more and 100,000 or less, more preferably 20,000 or more and 50,000 or less. If the viscosity-average molecular weight is less than 10,000, the mechanical strength of the resin is lowered, which is not practical. If the viscosity-average molecular weight is more than 300,000, it is difficult to apply an appropriate film thickness.

The polyarylate resin of the present invention can be mixed with other resins and used for an electrophotographic photosensitive member. Other resins mixed here include polymethyl methacrylate, polystyrene, vinyl polymers such as polyvinyl chloride, and copolymers thereof, polycarbonate,
Polyester, polysulfone, phenoxy, epoxy,
Examples include thermoplastic resins such as silicone resins and various thermosetting resins. Among these resins, polycarbonate resins are preferred.

<Electrophotographic Photoreceptor> The resin of the present invention described above is used for an electrophotographic photoreceptor, and is used as a binder resin in a photosensitive layer provided on a conductive support of the photoreceptor. Examples of the conductive support include a metal material such as aluminum, aluminum alloy, stainless steel, copper, and nickel, a metal, carbon, and a resin material to which conductivity is added by adding a conductive powder such as tin oxide, aluminum, or the like. Resins, glass, paper, and the like, in which a conductive material such as nickel or ITO (indium tin oxide alloy) is deposited or applied on the surface thereof, are mainly used. As the form, a drum shape, a sheet shape, a belt shape or the like is used. A conductive material having an appropriate resistance value may be applied on a conductive support made of a metal material for controlling conductivity and surface properties and for covering defects.

When a metal material such as an aluminum alloy is used as the conductive support, it may be used after anodizing treatment, chemical conversion treatment and the like. When the anodic oxidation treatment is performed, it is desirable to perform the sealing treatment by a known method. The surface of the support may be smooth, or may be roughened by using a special cutting method or performing a polishing treatment. Further, the support may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support.

An undercoat layer may be provided between the conductive support and the photosensitive layer in order to improve adhesion and blocking properties. As the undercoat layer, a resin, a material in which particles of a metal oxide or the like are dispersed in the resin, or the like is used. Examples of the metal oxide particles used for the undercoat layer include metal oxide particles containing one kind of metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, and titanium. Examples include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. One type of particles may be used alone, or a plurality of types of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. As the crystal form of the titanium oxide particles, any of rutile, anatase, Brookite, and amorphous can be used. A plurality of crystals may be included.

As the particle size of the metal oxide particles, various types can be used. Among them, from the viewpoint of characteristics and liquid stability, the average primary particle size is 10 nm or more and 100 nm or more.
The following is preferable, and particularly preferable is 10 nm or more and 25
nm or less. The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. As the binder resin used for the undercoat layer, phenoxy, epoxy, polyvinylpyrrolidone, polyvinyl alcohol, casein, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, polyamide, and the like alone or together with a curing agent are cured. Among them, alcohol-soluble copolymerized polyamides, modified polyamides and the like are preferable because they show good dispersibility and coatability.

The addition ratio of the inorganic particles to the binder resin can be arbitrarily selected, but it is preferable to use from 10% by weight to 500% by weight in view of the stability of the dispersion and the applicability. The thickness of the undercoat layer can be arbitrarily selected,
The thickness is preferably from 0.1 μm to 20 μm from the characteristics of the photoreceptor and the applicability. A known antioxidant may be added to the undercoat layer.

As the specific constitution of the photosensitive layer of the present invention, a charge generation layer containing a charge generation material as a main component, a charge transport material and a charge transport layer containing a binder resin as a main component are formed on a conductive support. Laminated photoconductors laminated in order. -An inverted two-layer type photoreceptor in which a charge transporting layer mainly composed of a charge transporting substance and a binder resin and a charge generating layer mainly containing a charge generating substance are laminated on a conductive support in this order.

A dispersion type photoreceptor in which a charge generation substance is dispersed in a layer containing a charge transport substance and a binder resin on a conductive support. The following is an example of the basic form. In the case of a stacked photoreceptor, examples of the charge generation material used for the charge generation layer include selenium and its alloys, cadmium sulfide, other inorganic photoconductive materials, phthalocyanine pigments,
Various photoconductive materials such as organic pigments such as azo pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthantrone pigments, and benzimidazole pigments can be used, and organic pigments, phthalocyanine pigments, and azo pigments are particularly preferred. These fine particles may be used, for example, polyester resin, polyvinyl acetate, polyacrylate, polymethacrylate, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, cellulose ester, cellulose ether. It is used in a form bound with various binder resins such as. The use ratio in this case is from 30 to 500 parts by weight with respect to 100 parts by weight of the binder resin, and the film thickness is usually 0.1 μm to 1 μm.
m, preferably 0.15 μm to 0.6 μm.

When a phthalocyanine compound is used as the charge generating substance, specifically, a metal-free phthalocyanine,
Metals such as copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, and germanium, or coordinated phthalocyanines such as oxides and halides thereof are used. Examples of the ligand to a trivalent or higher-valent metal atom include a hydroxyl group and an alkoxy group in addition to the oxygen atom and the chlorine atom shown above. Particularly preferred are highly sensitive X-type, τ-type nonmetal phthalocyanine, A-type, B-type, D-type and other titanyl phthalocyanines, vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, and the like. In addition, among the crystal forms of titanyl phthalocyanine mentioned here, A type and B type are described in W.C. These are shown as Phase I and Phase II by Heller et al. (Zeit. K
ristallogr. 159 (1982) 173), type A is what is known as a stable type. D type is powder X using CuKα ray.
In a line diffraction, the crystal form is characterized in that a diffraction angle 2θ ± 0.2 ° shows a clear peak at 27.3 °. The phthalocyanine compound may be a single compound or a mixture of several compounds. As the phthalocyanine compound or a mixed state that can be placed in a crystalline state here, the respective components may be mixed and used later, or the mixed state may be used in the manufacturing and processing steps of the phthalocyanine compound such as synthesis, pigmentation, and crystallization. It may be the one that has occurred. Such treatments include acid paste treatment and
Grinding treatment, solvent treatment and the like are known.

Examples of the charge transporting substance contained in the charge transporting layer include electron-withdrawing agents such as aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, and quinones such as diphenoquinone. Substances, carbazole derivatives, indole derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives,
Heterocyclic compounds such as oxadiazole derivatives, pyrazoline derivatives, thiadiazole derivatives, aniline derivatives, hydrazone compounds, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine compounds, those in which a plurality of these compounds are bonded, or those compounds And an electron donating substance such as a polymer having a group consisting of Among these, carbazole derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives and those in which a plurality of these derivatives are bonded are preferable, and those in which a plurality of aromatic amine derivatives, stilbene derivatives, butadiene derivatives are bonded, are preferable. preferable.

Specifically, those having a structure represented by the following general formula (12) are preferably used.

[0050]

Embedded image (In the general formula (12), Ar¹~ Ar^FourAre independent of each other
An arylene group which may have a substituent or a
Represents a good divalent heterocyclic group. Ar^Five, Ar⁶Is m ¹=
0, m^Two= 0, each of which may have a substituent.
Alkyl group, an aryl group which may have a substituent,
Represents a monovalent heterocyclic group which may have¹= 1, m^Two= 1
Is an alkylene group which may have a substituent,
An arylene group which may have a substituent or a
Represents a good divalent heterocyclic group. Q is a direct bond or divalent
Represents a residue. R¹~ R⁸Are each independently a hydrogen atom, a substituent
An alkyl group which may have a substituent, an ant which may have a substituent
A aralkyl group, which may have a substituent,
Represents a heterocyclic group which may be possessed. n¹~ N^FourAre each independently
Represents an integer of 0 to 4; Also, m¹, M^TwoAre each independently 0
Or represents 1. Also, Ar¹~ Ar⁶Are connected to each other
May be formed. ) In the general formula (12), R¹~ R⁸Are each independently a hydrogen atom,
An alkyl group which may have a substituent,
Aryl group which may be present, ara which may have a substituent
Represents an alkyl group or an optionally substituted heterocyclic group
However, as the alkyl group, for example, methyl group, ethyl
Group, propyl group, isopropyl group, butyl group, pentyl
Group, hexyl group, heptyl group, cyclopentyl group, cycle
And a rohexyl group.
Alkyl groups are preferred.

As the aryl group, a phenyl group,
Examples thereof include a tolyl group, a xylyl group, a naphthyl group and a pyrenyl group, and an aryl group having 6 to 12 carbon atoms is preferable. Examples of the aralkyl group include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 12 carbon atoms is preferable. Further, the heterocyclic group is preferably an aromatic heterocyclic ring, for example, a furyl group, a thienyl group, a pyridyl group and the like, and a monocyclic aromatic heterocyclic ring is more preferable.

Also, R¹~ R⁸In the most preferred
Are a methyl group and a phenyl group. Also, the general formula
(12) Medium, Ar¹~ Ar^FourEach independently has a substituent
May have an arylene group or a substituent
Represents a good divalent heterocyclic group, Ar ^Five, Ar⁶Is m¹=
0, m^TwoWhen = 0, each may have a substituent
Alkyl group, aryl group which may have a substituent,
Represents a monovalent heterocyclic group which may have a substituent;¹
= 1, m^TwoWhen = 1, even if each has a substituent
Good alkylene group, arylene optionally having substituent (s)
And a divalent heterocyclic group which may have a substituent.
However, as the aryl group, a phenyl group, a tolyl group,
A silyl group, a naphthyl group, a pyrenyl group, etc .;
Aryl groups of the formulas 6 to 14 are preferred;
Examples include phenylene group and naphthylene group.
A nylene group is preferred; the monovalent heterocyclic group is preferably an aromatic group;
Heterocycle having a property is preferable, for example, a furyl group, a thienyl
And a monocyclic aromatic heterocyclic ring.
More preferably, the divalent heterocyclic group has an aromatic property.
Are preferred, for example, a pyridylene group, a thienylene
Monocyclic aromatic heterocycles are more preferable.
No.

Of these, the most preferred is Ar ¹
And Ar ² are phenylene groups, and Ar ⁵ and Ar ⁶ are phenyl groups. Among the groups represented by R ^{1 to} R ⁸ and Ar ^{1 to} Ar ⁶ , an alkyl group, an aryl group, an aralkyl group,
The heterocyclic group may further have a substituent, and the substituent includes a cyano group; a nitro group; a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group,
Alkyl groups such as pentyl group, hexyl group, cyclopentyl group and cyclohexyl group; alkoxy groups such as methoxy group, ethoxy group and propyloxy group; alkylthio groups such as methylthio group and ethylthio group; alkenyl groups such as vinyl group and allyl group; Aralkyl groups such as benzyl group, naphthylmethyl group and phenethyl group; aryloxy groups such as phenoxy group and toloxy group; arylalkoxy groups such as benzyloxy group and phenethyloxy group; aryl groups such as phenyl group and naphthyl group; styryl group Arylvinyl groups such as phenyl, naphthylvinyl and the like; acyl groups such as acetyl and benzoyl; dialkylamino such as dimethylamino and diethylamino; diarylamino such as diphenylamino and dinaphthylamino; dibenzylamino ,
Diaralkylamino group such as diphenethylamino group, diheterocyclic amino group such as dipyridylamino group, dithienylamino group; substitution of diallylamino group or disubstituted amino group obtained by combining the above amino group substituents And an amino group.

Further, these substituents are bonded to each other to form
A cyclic hydrocarbon group or a heterocyclic group may be formed via a single bond, a methylene group, an ethylene group, a carbonyl group, a vinylidene group, an ethylenylene group, or the like. Of these, preferred substituents include a halogen atom, a cyano group, a hydroxyl group, and a group having 1 carbon atom.
Alkyl group of 6 to 6, alkoxy group of 1 to 6 carbon atoms, alkylthio group of 1 to 6 carbon atoms, aryloxy group of 6 to 12 carbon atoms, arylthio group of 6 to 12 carbon atoms, 2 carbon atoms
To 8 dialkylamino groups, a halogen atom,
An alkyl group having 1 to 6 carbon atoms and a phenyl group are more preferable, and a methyl group and a phenyl group are particularly preferable.

In the general formula (12), n ^{1 to} n ⁴ each independently represent an integer of 0 to 4, preferably 0 to 2, and most preferably 1. m ¹ and m ² represent 0 or 1, and 0 is preferred. In the general formula (12), Q represents a direct bond or a divalent residue, and a preferable divalent residue is a group 16 atom, an alkylene which may have a substituent, or a substituent. Arylene group which may be, a cycloalkylidene group which may have a substituent, or these are bonded to each other, for example,
[-O-A-O-], [-A-O-A-], [-S-A-S-S
-], [-AA-] and the like (provided that A represents an arylene group which may have a substituent or an alkylene group which may have a substituent).

As the alkylene group constituting Q, those having 1 to 6 carbon atoms are preferable, and among them, a methylene group and an ethylene group are more preferable. The cycloalkylidene group preferably has 5 to 8 carbon atoms, and more preferably a cyclopentylidene group and a cyclohexylidene group. The arylene group preferably has 6 to 14 carbon atoms, and among them, a phenylene group and a naphthylene group are more preferable.

The alkylene group, arylene group and cycloalkylidene group may have a substituent.
Preferred substituents include a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms. These charge transporting substances may be used alone or in combination. The charge transport layer is formed in a state where these charge transport materials are bound to the binder resin. The charge transport layer may be composed of a single layer, or may be a layer in which a plurality of layers having different constituent components or composition ratios are stacked.

The ratio between the binder resin and the charge transporting material is
Usually, 30 to 20 parts by weight based on 100 parts by weight of the binder resin.
0 parts by weight, preferably in the range of 40 to 150 parts by weight. The thickness is generally 5 to 50 μm, preferably 1 to 50 μm.
It is preferably from 0 to 45 μm. The charge transport layer has a well-known plasticizer, an antioxidant, an ultraviolet absorber, and an electron-attracting property in order to improve film formability, flexibility, coating properties, stain resistance, gas resistance, light resistance, and the like. Additives such as compounds and leveling agents may be included.

Examples of antioxidants include hindered phenol compounds and hindered amine compounds. In the case of the dispersion type photosensitive layer, the above-mentioned charge generating substance is dispersed in the charge transporting medium having the above-described mixing ratio. In this case, the particle size of the charge generating substance needs to be sufficiently small, preferably 1 μm or less, more preferably 0.5 μm or less.
Used below μm. If the amount of the charge generating substance dispersed in the photosensitive layer is too small, sufficient sensitivity cannot be obtained. If the amount is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. %, More preferably in the range of 1 to 20% by weight.

The thickness of the photosensitive layer is usually 5 to 50 μm, more preferably 10 to 45 μm. Also in this case, a known plasticizer for improving film forming property, flexibility, mechanical strength, etc., an additive for suppressing residual potential, a dispersing aid for improving dispersion stability, a coating property. Leveling agents, surfactants such as silicone oil,
Fluorine-based oil and other additives may be added.

A protective layer may be provided on the photosensitive layer for the purpose of preventing the photosensitive layer from being worn and preventing or reducing the deterioration of the photosensitive layer due to a discharge product or the like generated from a charger or the like. Also, in order to reduce the frictional resistance and wear of the photoconductor surface,
The surface layer may contain a fluorine resin, a silicone resin, or the like. Further, particles of these resins or particles of an inorganic compound may be included.

Each of the layers constituting the photoreceptor is formed by dip coating, spray coating, nozzle coating, bar coating, roll coating, blade coating or the like on a support. As a method for forming each layer, a known method such as sequentially applying a coating solution obtained by dissolving or dispersing a substance to be contained in a layer in a solvent can be applied.

An electrophotographic apparatus such as a copying machine or a printer using the electrophotographic photosensitive member of the present invention has at least a charge,
Although each of the processes includes exposure, development, and transfer, any of the processes may be used for each process. As a charging method (charging device), for example, any of corotron or scorotron charging using corona discharge, contact charging using a conductive roller, a brush, a film, or the like may be used. Of these, in the charging method using corona discharge, scorotron charging is often used to keep the dark area potential constant. As a developing method, a general method of developing by contacting or non-contacting a magnetic or non-magnetic one-component developer, a two-component developer or the like is used. The transfer method may be any of a method using corona discharge, a method using a transfer roller or a transfer belt, and the like. The transfer may be performed directly on paper, an OHP film, or the like, or may be performed once on an intermediate transfer member (belt or drum shape) and then transferred onto paper or an OHP film.

Usually, after the transfer, a fixing process for fixing the developer onto paper or the like is used, and as a fixing means, generally used heat fixing, pressure fixing and the like can be used. In addition to these processes, a process that is generally used, such as cleaning and static elimination, may be provided.

[0065]

The present invention will be described below in more detail with reference to Production Examples, Examples and Comparative Examples. The present invention is not limited to the manufacturing method according to the manufacturing example shown here. <Production of polyarylate resin> [Viscosity average molecular weight] A polyarylate resin was dissolved in dichloromethane to prepare a solution having a concentration C of 6.00 g / L.
The falling time t ₀ of the solvent (dichloromethane) is 136.16.
The falling time t of the sample solution was measured in a thermostatic water bath set at 20.0 ° C. using an Ubbelohde capillary viscometer for 2 seconds. The viscosity average molecular weight Mv was calculated according to the following equation. a = 0.438 × η _sp +1 η _sp = t / t ₀ −1 b = 100 × η _sp / C C = 6.00 (g / L) η = b / a Mv = 3207 × η ¹ . ²⁰⁵

Production Example 1 (Method for Producing Polyarylate Resin A of Comparative Example 1) Sodium hydroxide (7.26 g) and water (600 ml) were weighed into a 1 L beaker, and dissolved by stirring while bubbling with nitrogen. Thereto, p-tert-butylphenol (0.5463 g), benzyltriethylammonium chloride (0.089 g) and bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (17.86 g) were added. After stirring, the aqueous alkali solution was transferred to a 1 L reaction tank.

Separately, terephthalic acid chloride (14.4)
5 g) was dissolved in dichloromethane (300 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 1 hour. After stirring was further continued for 3 hours, acetic acid (2.39 ml) and dichloromethane (150 ml) were added, and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. The organic layer was washed once with a 0.1 N aqueous sodium hydroxide solution (340 ml), then twice with 0.1 N hydrochloric acid (340 ml), and twice with water (340 ml). went.

The organic layer after washing was washed with methanol (2,500 m
The precipitate obtained by pouring in 1) was taken out by filtration, and dried to obtain a target polyarylate resin A. The viscosity average molecular weight of the obtained polyarylate resin A was 32,200. The structural formula is shown below.

[0069]

Embedded image Production Example 2 (Production Method of Polyarylate Resin B of Comparative Example 2) Sodium hydroxide (5.20 g) and water (400 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, p-tert-butylphenol (0.2173 g), benzyltriethylammonium chloride (0.0647 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (6.31 g) and bis (4-hydroxyphenyl) methane [bisphenol F] (4.93
After adding g) and stirring, the aqueous alkali solution was transferred to a 1 L reaction tank.

Separately, terephthalic acid chloride (10.1
5 g) was dissolved in dichloromethane (200 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 1 hour. After stirring was further continued for 3 hours, acetic acid (1.71 ml) and dichloromethane (100 ml) were added and stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. The organic layer was washed once with a 0.1 N aqueous sodium hydroxide solution (210 ml), then twice with 0.1 N hydrochloric acid (210 ml), and twice with water (210 ml). went.

The washed organic layer was washed with methanol (2000 m
The precipitate obtained by pouring in 1) was taken out by filtration, and dried to obtain a target polyarylate resin B. The viscosity average molecular weight of the obtained polyarylate resin B was 33,700. The structural formula is shown below.

[0072]

Embedded image Production Example 3 (Production Method of Polyarylate Resin C of Comparative Example 3) Sodium hydroxide (15.62 g) and water (1120 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.1953 g) and bis (4-hydroxyphenyl) methane [p, p'-BPF], (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o, p'-BP
F], bis (2-hydroxymethylphenyl) methane [o,
o'-BPF] [BPF-D manufactured by Honshu Chemical Co., Ltd .;
p ′: o, p ′: o, o ′ = about 35:48:17] (2
After adding 9.44 g) and stirring, the aqueous alkali solution was transferred to a 2 L reaction tank. Thereafter, p-tert-butylphenol (0.8833 g) was added.

Separately, terephthalic acid chloride (30.4
8 g) was dissolved in dichloromethane (560 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (5.15 ml) was added and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1N aqueous sodium hydroxide solution (560 m
1) washing once, then 0.1N hydrochloric acid (420m
The washing was performed twice in 1), and the washing was further performed twice with water (420 ml).

The washed organic layer was washed with methanol (3000 m
The precipitate obtained by pouring in l) was taken out by filtration, and dried to obtain a target polyarylate resin C. The viscosity average molecular weight of the obtained polyarylate resin C was 19,100. The structural formula is shown below.

[0075]

Embedded image Production Example 4 (Production Method of Polyarylate Resin D of Example 1) Sodium hydroxide (14.01 g) and water (1120 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.1744 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (23.79 g) and bis (4-
Hydroxyphenyl) methane [p, p'-BPF], (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o,
p'-BPF], a mixture of bis (2-hydroxymethylphenyl) methane [o, o'-BPF] [BPF- manufactured by Honshu Chemical Co., Ltd.]
D; p, p ': o, p': o, o '= about 35: 48: 1
7] (7.96 g) was added and stirred, and then the alkaline aqueous solution was transferred to a 2 L reaction tank. Then 2,6-dimethyl-4-tert-butyl-phenol (0.712 g)
Was added.

Separately, terephthalic acid chloride (27.3)
5 g) was dissolved in dichloromethane (560 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (4.62 ml) was added and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1N aqueous sodium hydroxide solution (560 m
1) washing once, then 0.1N hydrochloric acid (420m
The washing was performed twice in 1), and the washing was further performed twice with water (420 ml).

The organic layer after washing was washed with methanol (3000 m
The precipitate obtained by pouring in 1) was taken out by filtration, and dried to obtain a target polyarylate resin D. The viscosity average molecular weight of the obtained polyarylate resin D was 36,700. The structural formula is shown below.

[0078]

Embedded image Production Example 5 (Production method of polyarylate resin E of Example 2) Sodium hydroxide (7.19 g) and water (560 ml) were weighed into a 1 L beaker, and dissolved by stirring while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.0899 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (8.68 g), bis (4-hydroxyphenyl) methane [p, p '-BPF] (4.75 g) and (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o, p'-BPF] (2.03 g) were added and stirred. Moved to Thereafter, 4-tert-butyl-2,6-dimethylphenol (0.4827 g) was added.

Separately, terephthalic acid chloride (14.0
4g) was dissolved in dichloromethane (280 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (2.37 ml) was added and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1 N aqueous sodium hydroxide solution (280 m
1) washing once, then 0.1N hydrochloric acid (210m
The washing was performed twice in 1), and the washing was further performed twice with water (210 ml).

The washed organic layer was washed with methanol (1500 m
The precipitate obtained by pouring into 1) was taken out by filtration, and dried to obtain a target polyarylate resin E. The viscosity average molecular weight of the obtained polyarylate resin E was 33,300. The structural formula is shown below.

[0081]

Embedded image Production Example 6 (Production method of polyarylate resin F of Example 3) Sodium hydroxide (14.46 g) and water (1120 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.1791 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (17.62 g), bis (4-hydroxyphenyl) methane [p, p '-BPF], (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o, p'-BP
F], bis (2-hydroxymethylphenyl) methane [o,
o'-BPF] [BPF-D manufactured by Honshu Chemical Co., Ltd .;
p ′: o, p ′: o, o ′ = about 35:48:17]
(6.88 g) and bis (4-hydroxyphenyl)
After adding methane [p, p'-BPF] (6.88 g) and stirring,
This aqueous alkali solution was transferred to a 1 L reaction tank. Then 4-
Tert-butyl-phenol (0.4129 g) was added.

Separately, terephthalic acid chloride (28.2)
2 g) was dissolved in dichloromethane (560 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (4.77 ml) was added, and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1N aqueous sodium hydroxide solution (560 m
1) washing once, then 0.1N hydrochloric acid (420m
The washing was performed twice in 1), and the washing was further performed twice with water (420 ml).

The organic layer after washing was washed with methanol (3000 m
The precipitate obtained by pouring into 1) was taken out by filtration, and dried to obtain a target polyarylate resin F. The viscosity average molecular weight of the obtained polyarylate resin F was 44,700. The structural formula is shown below.

[0084]

Embedded image Production Example 7 (Production method of polyarylate resin G of Example 4) Sodium hydroxide (7.22 g) and water (560 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.0894 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (8.79 g), bis (4-hydroxyphenyl) methane [p, p '-BPF] (3.44 g) and bis (2-hydroxyphenyl) methane [o, o'-BPF] (3.
After adding 44 g) and stirring, the aqueous alkali solution was added to 1
Transferred to L reactor. Then 4-tert-butyl-2,
6-Dimethylphenol (0.2446 g) was added.

Separately, terephthalic acid chloride (14.0
9 g) was dissolved in dichloromethane (280 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (2.38 ml) was added and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1 N aqueous sodium hydroxide solution (280 m
1) washing once, then 0.1N hydrochloric acid (210m
The washing was performed twice in 1), and the washing was further performed twice with water (210 ml).

The washed organic layer was treated with methanol (1500 m
The precipitate obtained by pouring into 1) was taken out by filtration, and dried to obtain a target polyarylate resin G. The viscosity average molecular weight of the obtained polyarylate resin G was 46,400. The structural formula is shown below.

[0087]

Embedded image Production Example 8 (Production Method of Polyarylate Resin H of Example 5) Sodium hydroxide (14.46 g) and water (1120 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.1791 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (17.62 g) and bis (4-
Hydroxyphenyl) methane [p, p'-BPF], (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o,
p'-BPF], a mixture of bis (2-hydroxymethylphenyl) methane [o, o'-BPF] [BPF- manufactured by Honshu Chemical Co., Ltd.]
D; p, p ': o, p': o, o '= about 35: 48: 1
7] (13.76 g) was added and stirred, and then the alkaline aqueous solution was transferred to a 2 L reaction tank. Then p-tert-
Butylphenol (0.4129 g) was added.

Separately, terephthalic acid chloride (28.2)
2 g) was dissolved in dichloromethane (560 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (4.77 ml) was added, and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1N aqueous sodium hydroxide solution (560 m
1) washing once, then 0.1N hydrochloric acid (420m
The washing was performed twice in 1), and the washing was further performed twice with water (420 ml).

The organic layer after washing was washed with methanol (3000 m
The precipitate obtained by pouring into l) was taken out by filtration, and dried to obtain a target polyarylate resin H. The viscosity average molecular weight of the obtained polyarylate resin H was 29,800. The structural formula is shown below.

[0090]

Embedded image Production Example 9 (Method for Producing Polyarylate Resin I of Comparative Example 4) Sodium hydroxide (7.44 g) and water (560 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.0930 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (5.39 g), bis (4-hydroxyphenyl) methane [p, p '-BPF] (6.87 g) and (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o, p'-BPF] (2.95 g) were added and stirred. Moved to Then 4-tert-butyl-2,6-dimethylphenol (0.4209 g) was added.

Separately, terephthalic acid chloride (14.5)
2g) was dissolved in dichloromethane (280 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (2.45 ml) was added and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1 N aqueous sodium hydroxide solution (280 m
1) washing once, then 0.1N hydrochloric acid (210m
The washing was performed twice in 1), and the washing was further performed twice with water (210 ml).

The washed organic layer was washed with methanol (1500 m
The precipitate obtained by pouring into 1) was taken out by filtration, and dried to obtain a target polyarylate resin I. The viscosity average molecular weight of the obtained polyarylate resin I was 33,500. The structural formula is shown below.

[0093]

Embedded image Production Example 10 (Production method of polyarylate resin K of Example 6) Sodium hydroxide (13.62 g) and water (1120 ml) were weighed into a 1 L beaker, and stirred and dissolved while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.1703 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (29.58 g) and bis (4-
Hydroxyphenyl) methane [p, p'-BPF], (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o,
p'-BPF], a mixture of bis (2-hydroxymethylphenyl) methane [o, o'-BPF] [BPF- manufactured by Honshu Chemical Co., Ltd.]
D; p, p ': o, p': o, o '= about 35: 48: 1
7] (2.57 g) was added and stirred, and then the aqueous alkali solution was transferred to a 2 L reaction tank. Thereafter, 2,3,6-trimethylphenol (0.6984 g) was added.

Separately, terephthalic acid chloride (26.5)
8 g) was dissolved in dichloromethane (560 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (4.49 ml) was added and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1N aqueous sodium hydroxide solution (560 m
1) washing once, then 0.1N hydrochloric acid (420m
The washing was performed twice in 1), and the washing was further performed twice with water (420 ml).

The washed organic layer was washed with methanol (3000 m
The precipitate obtained by pouring into l) was taken out by filtration, and dried to obtain a target polyarylate resin K. The viscosity average molecular weight of the obtained polyarylate resin K was 40,700. The structural formula is shown below.

[0096]

Embedded image Production Example 11 (Example 7: Method for producing polyarylate resin L) In a 1 L beaker, sodium hydroxide (14.92 g) and water (1120 ml) were weighed, and dissolved by stirring while bubbling with nitrogen. There, benzyltriethylammonium chloride (0.1848 g), bis (4-hydroxy-3,5-dimethylphenyl) methane [tetramethylbisphenol F] (10.91 g) and bis (4-
Hydroxyphenyl) methane [p, p'-BPF], (2-hydroxyphenyl) (4-hydroxyphenyl) methane [o,
p'-BPF], a mixture of bis (2-hydroxymethylphenyl) methane [o, o'-BPF] [BPF- manufactured by Honshu Chemical Co., Ltd.]
D; p, p ': o, p': o, o '= about 35: 48: 1
7] (19.88 g) was added and stirred, and then the aqueous alkali solution was transferred to a 2 L reaction tank. Then p-tert-
Butylphenol (0.4260 g) was added.

Separately, terephthalic acid chloride (29.1)
1 g) was dissolved in dichloromethane (560 ml) and transferred into a dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C., while stirring the aqueous alkali solution in the reaction tank, a dichloromethane solution was dropped from the dropping funnel over 30 minutes. After stirring was further continued for 4 hours, acetic acid (4.92 ml) was added and the mixture was stirred for 30 minutes. Thereafter, the stirring was stopped and the organic layer was separated. This organic layer was washed with a 0.1N aqueous sodium hydroxide solution (560 m
1) washing once, then 0.1N hydrochloric acid (420m
The washing was performed twice in 1), and the washing was further performed twice with water (420 ml).

The washed organic layer was washed with methanol (3000 m
The precipitate obtained by pouring into 1) was taken out by filtration, and dried to obtain a target polyarylate resin L. The viscosity average molecular weight of the obtained polyarylate resin L was 27,200. The structural formula is shown below.

[0099]

Embedded image <Production of Photoconductor> Example 1 10 parts by weight of β-type oxytitanium phthalocyanine having the following structure was added to 4-methoxy-4-methylpentanone-
2 In addition to 150 parts by weight, pulverization and dispersion treatment was performed by a sand grind mill.

[0100]

Embedded image In addition, polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd.,
5% of brand name Denka butyral # 6000C) 1,2
-100 parts of dimethoxyethane solution and 5% of phenoxy resin (PKHH, manufactured by Union Carbide Co.)
A binder solution was prepared by mixing 100 parts of a 1,2-dimethoxyethane solution.

In 160 parts by weight of the previously prepared pigment dispersion,
100 parts by weight of a binder solution and an appropriate amount of 1,2-dimethoxyethane were added to finally prepare a dispersion having a solid content of 4.0%. The thus obtained dispersion was applied on a polyethylene terephthalate film on which aluminum was vapor-deposited on the surface so as to have a thickness of 0.4 μm to provide a charge generation layer. Next, on this film, 50 parts by weight of the following hole transporting compound [1]

[0102]

Embedded image And polyarylate resin D100 produced in Production Example 4
Parts by weight, 8 parts by weight of an antioxidant (Irganox 1076), and 0.0% of silicone oil as a leveling agent.
A solution obtained by dissolving 3 parts by weight in 640 parts by weight of a mixed solvent of tetrahydrofuran and toluene (tetrahydrofuran 80% by weight, toluene 20% by weight) is applied and dried at 125 ° C. for 20 minutes, and the film thickness after drying becomes 20 μm. The charge transport layer was provided as described above. At this time, the solubility of the polyarylate resin D in a mixed solvent of tetrahydrofuran and toluene was good. The coating solution did not show any change such as solidification even after being left at room temperature for one week. Table 2 shows the results of the solubility and solution stability.

Examples 2 to 7 and Comparative Examples 1 to 4 The same operation as in Example 1 was performed, except that the polyarylate resin in Example 1 was replaced with the polyarylate resin produced in each of the production examples. Table 2 shows the results of the solubility and solution stability of these resins.

The obtained photosensitive members were evaluated as follows. [Friction test] The toner was placed on the photoreceptor prepared above at 0.1%.
1 cm / cm ² of urethane rubber of the same material as the cleaning blade on the surface to be uniformly placed and contacted to 1 mg / cm ²
It is used at an angle of 45 degrees and cut at a load of 20
The 100th kinetic friction coefficient when urethane rubber was moved 100 times at 0 g, at a speed of 5 mm / sec, and a stroke of 20 mm was measured with a fully automatic friction and wear tester DFPM-SS manufactured by Kyowa Interface Chemical Co., Ltd. Table 2 shows the results. [Abrasion Test] The photoreceptor film was cut into a circle having a diameter of 10 cm, and abrasion was evaluated using a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.). The test conditions were as follows: The wear amount after 1000 rotations without load (self-weight of the wear wheel) was measured by comparing the weight before and after the test with a wear wheel CS-10F in an atmosphere of 23 ° C. and 50% RH without using a load (the weight of the wear wheel). did. Table 2 shows the results.

[Electrical Characteristics] An electrophotographic characteristic evaluation apparatus manufactured according to the Electrophotographic Society of Japan measurement standard (Basic and Application of Electrophotographic Technology, edited by the Electrophotographic Society, Corona, 404-40)
5), the photoreceptor was attached to an aluminum drum to form a cylinder, and the aluminum drum and the aluminum base of the photoreceptor were electrically connected to each other. An electrical property evaluation test was performed by a cycle of charging, exposure, potential measurement, and static elimination. that time,
The initial surface potential is -700 V, monochromatic light of 780 nm for exposure and 660 nm for static elimination, and light of 780 nm is used for 2.
The surface potential (VL) at the time of irradiation of 4 μJ / cm ² was measured. In the VL measurement, the time required for the exposure-potential measurement was 139 ms. The measurement environment was a temperature of 25 ° C. and a relative humidity of 50% (VL: NN), and a temperature of 5 ° C. and a relative humidity of 1
Performed under 0% (VL: LL). This surface potential (VL)
Indicates that the smaller the absolute value of the value, the better the response. Table 2 shows the results.

From the above results, the polyarylate resin having a specific structure has high solubility and solution stability even in a non-halogen solvent and, by using this, has excellent mechanical properties, abrasion resistance and slipperiness. It can be seen that an electrophotographic photoreceptor having excellent electrical characteristics, particularly excellent responsiveness, can be obtained.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

The electrophotographic photoreceptor resin of the present invention has sufficient mechanical properties by using a polyarylate resin having a specific structure, has high solubility in non-halogen solvents, and has good electrical properties. Excellent in characteristics, especially responsiveness.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/06 321 G03G 5/06 321 (72) Inventor Chiyoko Sato 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Co., Ltd. (72) Inventor, Akira Teruaki, Kanagawa Prefecture, Yokohama City, Aoba-ku, 1000 Kamoshita-cho, Mitsubishi, Japan Mitsubishi Chemical Co., Ltd. F-term (reference) 2H068 AA13 AA20 BA13 BA16 BA21 BB27 BB52

Claims (9)

[Claims] 1. An electrophotographic photoreceptor having at least a photosensitive layer on a conductive substrate, wherein the binder resin of the photosensitive layer has a polyarylate structure represented by the following general formula (1). Electrophotographic photoreceptor. Embedded image (The structure represented by the following general formula (2) in the general formula (1) is at least one selected from the structures represented by the following general formula (3).) Embedded image (A and b in the general formula (3) are 0 ≦ a ≦ 1, 0 ≦ b
≦ 1 and a + b = 1. (In addition, the structure represented by the following general formula (4) in the general formula (1) is at least two types selected from the structures represented by the following general formulas (5), (6) and (7). There is.) Embedded image Embedded image Embedded image (In addition, x and y in the general formula (1) are values indicating amounts in the resin.) (Also, the general bisphenol component in all bisphenol components constituting the polyarylate structure represented by the general formula (1) (The structural component represented by the formula (5) does not exceed 45%.) 2. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive substrate, wherein the binder resin of the photosensitive layer has a polyarylate structure represented by the following general formula (8). Electrophotographic photoreceptor. Embedded image (In the general formula (8), x and y are values indicating the amount in the resin.) (The structure represented by the following general formula (4) in the general formula (8) is represented by the following general formula ( (5), (6), and at least two types selected from the structures represented by (7).) Embedded image Embedded image Embedded image (The structural component represented by the general formula (5) does not exceed 45% of all the bisphenol components constituting the polyarylate structure represented by the general formula (8).) 3. An electrophotographic photoreceptor having at least a photosensitive layer on a conductive substrate, wherein the binder resin of the photosensitive layer has the following general formula (9) in addition to the polyarylate structure represented by the following general formula (9): (10) An electrophotographic photosensitive member having at least one of the structures represented by (11). Embedded image Embedded image Embedded image (In the general formula, m, n, o, and p are values indicating the amount in the resin, and 0 <n / (m + n + o + p) ≦ 0.45.) 4. In the general formulas (9), (10) and (11),
4. The electrophotographic photosensitive member according to claim 3, wherein m, n, o, and p are values in a range satisfying the following expression. 0.2 ≦ m / (m + n + o + p) ≦ 0.8 0.01 ≦ n / (m + n + o + p) <0.40 ≦ o / (m + n + o + p) <0.30 ≦ p / (m + n + o + p) <0.3 and 0 0.7 ≦ (m + n) / (m + n + o + p) ≦
0.95 0.05 ≦ (o + p) / (m + n + o + p) ≦ 0.3 5. In the general formulas (9), (10) and (11),
4. The electrophotographic photosensitive member according to claim 3, wherein m, n, o, and p are values in a range satisfying the following expression. 0.3 ≦ m / (m + n + o + p) ≦ 0.7 0.1 ≦ n / (m + n + o + p) <0.40 ≦ o / (m + n + o + p) <0.20 ≦ p / (m + n + o + p) <0.1 and 0 .8 ≦ (m + n) / (m + n + o + p) ≦
0.9 0.1 ≦ (o + p) / (m + n + o + p) ≦ 0.2 6. The electrophotographic photosensitive member according to claim 1, wherein the resin having a polyarylate structure has a viscosity average molecular weight of 15,000 to 100,000. 7. A charge transporting material containing at least one selected from the group consisting of a carbazole derivative, a hydrazone derivative, an aromatic amine derivative, a stilbene derivative, a butadiene derivative, and a combination of a plurality of these derivatives. 7. The electrophotographic photosensitive member according to any one of items 1 to 6. 8. The charge-transporting material is an aromatic amine derivative,
The electrophotographic photoreceptor according to claim 7, wherein a plurality of stilbene derivatives and butadiene derivatives are bonded. 9. The charge-transporting material contains a material having a structure represented by the following general formula (12).
2. The electrophotographic photoreceptor according to 1. Embedded image (In the general formula (8), Ar ^{1 to} Ar ⁴ each independently represent an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Ar ⁵ , Ar ⁶ is m ¹ = 0,
When m ² = 0, each represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent, and m ¹ When = 1 and m ² = 1, it represents an alkylene group which may have a substituent, an arylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent. Q represents a direct bond or a divalent residue. R ^{1 to} R ⁸ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. Represents an optionally substituted heterocyclic group. n ^{1 to} n ⁴ are each independently 0 to
Represents an integer of 4. M ¹ and m ² each independently represent 0 or 1. Ar ^{1 to} Ar ⁶ may be bonded to each other to form a cyclic structure. )