JP3228177B2 - Electrophotographic photoreceptor and electrophotographic apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to relates to an electrophotographic photoreceptor and an electrophotographic apparatus using the utility of Ah Lupo Li <br/> carbonate resin.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors (hereinafter simply referred to as "photoreceptors")
Is often used in electrophotographic devices such as copiers and laser beam printers because of the advantages that high speed and high printing quality can be obtained. The electrophotographic photoreceptor used in such an electrophotographic apparatus is manufactured at a lower cost than the conventional electrophotographic photoreceptor using an inorganic photoconductive material such as selenium, selenium-tellurium alloy, selenium-arsenic alloy, and cadmium sulfide. In recent years, an electrophotographic photosensitive member using an organic photoconductive material having an excellent advantage in terms of performance and waste property (hereinafter, simply referred to as “organic photosensitive member”) has become mainstream in recent years.

[0003] Among them, a function-separated type organic photoconductor in which a charge generation layer that generates electric charges by exposure and a charge transport layer that transports electric charges are laminated, has characteristics of electrophotography such as sensitivity / charging property and repetition stability. In view of this, various proposals have been made and put to practical use. Further, as a binder resin for the photosensitive layer of these photoconductors, a polycarbonate resin is particularly preferable because it has excellent properties such as mechanical strength.

[0004]

Since an electrophotographic photosensitive member usually repeats processes such as charging, exposure, development, transfer, and cleaning, it is required to maintain stable characteristics. However, the charging device using corona discharge (corotron, scorotron) is used, the charge transport material of the photosensitive member surface layer is deteriorated by ozone and NO _X, etc. generated from the charger, a reduction in sensitivity, variation of residual potential, Deterioration of charging ability and image blur occur. In addition, relatively ozone and NO _x
Even if a contact charger with less occurrence of odor is used, the charge transporting substance in the surface layer is deteriorated, and the above-mentioned trouble occurs.

Therefore, it has been proposed to add an antioxidant to stabilize the characteristics of the electrophotographic photosensitive member (Japanese Patent Publication No. 6-75205, Japanese Patent No. 25317).
No. 40). However, the inclusion of an antioxidant causes a decrease in sensitivity, an increase in residual potential, and deterioration of cycle characteristics. The occurrence of fogging, a decrease in contrast, and bleeding, which is precipitation of the antioxidant, occur during running, resulting in low near-surface. An increase in the molecular weight component causes a problem that the abrasion resistance is reduced, the concentration of the antioxidant in the photosensitive layer is reduced, and the antioxidant function is lost during running.

Further, it has been proposed to use a resin obtained by copolymerizing a structure of an antioxidant such as hindered phenol as a binder resin for an electrophotographic photoreceptor surface layer (Japanese Patent Application Laid-Open No. Hei 8-
311190, JP-A No. 8-311191, JP-
JP 8-31193), believed antioxidant function by copolymerizing is lost, i.e., when it is copolymerized hindered phenol becomes not a hindered phenol structure, separately oxide Inhibitors need to be added.

[0007] The present invention has been made in view of the above situation, and has as its object to solve the above-mentioned problems in the prior art. That is, an object of the present invention is to provide an electrophotographic photosensitive member and an electrophotographic apparatus which are excellent in stability upon repeated use.

[0008]

As a result of various studies in view of the above points, the present inventors have found that at least a polycarbonate resin having a hindered phenol structure or a hindered amine structure at the terminal thereof has a stable antioxidant function for a long period of time. And the use of the polycarbonate resin as a binder resin for a photosensitive layer of an electrophotographic photoreceptor to provide stability and durability when repeatedly used. With respect to the present invention, it has been found that it has extremely excellent characteristics and can solve the problem of deterioration of the repetition stability of the photosensitive layer when repeatedly rotated for a long period of time in an electrophotographic apparatus, thereby completing the present invention. .

That is, the present invention provides: (1) an electrophotographic method comprising providing a photosensitive layer on a conductive support;
In the photoconductor, the photosensitive layer is formed of a polycarbonate resin represented by the following general formula (I) (hereinafter, referred to as “a specific polycarbonate).
Resin ". ) Containing an electron
It is a photoreceptor . -General formula (I)

[0010]

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(In the above formula, at least one of the terminal groups of X ₁ and X ₂ represents a group selected from a group having a hindered phenol structure and a group having a hindered amine structure. Represents a necessary group, and p represents an integer capable of making the viscosity average molecular weight of the entire polycarbonate resin in a range of 3000 to 300,000. )

(2) At least one of the terminal groups of X ₁ and X _{2 in} the general formula (I) has a hindered phenol structure represented by the following general formula (II): 20. An electrophotographic photosensitive member according to any one of the preceding claims .・ General formula (II)

[0013]

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(In the above formula, R ₁ and R ₈ each represent a branched alkyl group, R _{2 to} R ₇ each independently represent hydrogen, an alkyl group, an aryl group or an alkoxy group, and n represents 1 to
Represents an integer of 3, and Y ₁ is a linking group represented by the following structural formula .
Selected from

[0015]

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(In the above formula, R _{9 to} R ₁₃ are each independently
Represent hydrogen, alkyl, aryl, and alkoxy groups
And a represents an integer of 0 to 10. ))

(3) Invention ( ₁ ) wherein at least one of the terminal groups of X ₁ and X _{2 in} the general formula (I) has a hindered phenol structure represented by the following general formula (III): 2. The electrophotographic photosensitive member according to item 1.・ General formula (III)

[0018]

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(In the above formula, at least one of R ₁₄ and R ₁₅ represents a branched alkyl group, the rest represents an alkyl group, an aryl group or an alkoxy group, and at least one of R ₁₆ and R ₁₇ represents a branched alkyl group. And the rest represent an alkyl group, an aryl group or an alkoxy group, b and c each independently represent an integer of 1 to 3, m represents an integer of 1 to 3, and A represents -O- or -NH-. , Y ₂ is represents a linking group or a single bond.)

(4) The invention described in (1), wherein at least one of the terminal groups of X ₁ and X _{2 in} the general formula (I) has a hindered amine structure represented by the following general formula (IV). Electrophotographic photoreceptor .・ General formula (IV)

[0021]

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(In the above formula, at least one of Q _{1 to} Q ₃ is a group represented by the following structural formula,

[0023]

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The remainder is an alkyl group or the following structural formula

[0025]

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Wherein Q ₄ represents hydrogen or an alkyl group having 1 to 13 carbon atoms. )

(5) The invention (1) wherein at least one of the terminal groups of X ₁ and X _{2 in} the general formula (I) has a hindered amine structure represented by the following general formula (V): Electrophotographic photoreceptor .・ General formula (V)

[0028]

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(In the above formula, n represents an integer that allows the viscosity average molecular weight of the entire polycarbonate resin to fall within a range of 3000 to 300,000. )

(6) The invention according to any one of the inventions (1) to (5), wherein R in the general formula (I) is represented by a structural unit represented by the following general formula (VI). Electrophotographic exposure
Body .・ General formula (VI)

[0031]

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(In the above formula, R _{18 to} R ₂₁ each independently represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 1 to 1 carbon atoms.
5 alkoxy groups, and these groups may be substituted. Z represents a group represented by the following structural formula.

[0033]

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(In the above formula, R _{22 to} R ₂₉ each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or R
₂₂ and R ₂₃ , R ₂₆ and R ₂₈ or R ₂₇ and R ₂₉ are bonded together to form a group forming a carbocyclic or heterocyclic ring, and these groups may be substituted. d represents 0 or 1. ))

(7) The electrophotographic photosensitive material according to any one of the inventions (1) to (5), wherein R in the general formula (I) is represented by a structural unit represented by the following structural formula. Body .

[0036]

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( 8 ) The invention as described in any one of the above items (1) to (7) , wherein the photosensitive layer has a single-layer structure containing both a charge transport material and a charge generation material in the same layer. Electrophotographic photoreceptor.

( 9 ) The invention characterized in that the photosensitive layer is functionally separated into a charge transport layer containing at least a charge transport material and a charge generation layer containing a charge generation material.
The electrophotographic photosensitive member according to any one of (1) to (7) .

( 10 ) The electrophotographic photoreceptor according to the invention (8) or (9) , wherein a benzidine compound represented by the following general formula (VII) is contained in the photosensitive layer as a charge transporting material. is there.・ General formula (VII)

[0040]

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(In the above formula, R ₃₀ and R ₃₀ ′ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, and R ₃₁ , R ₃₁ ′, R ₃₂ and R ₃₂ 'May be the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group, and e, e', f, and f 'each independently represent an integer of 1 or 2. Represents. )

( 11 ) The invention (8) or (9) , wherein the photosensitive layer contains a triarylamine compound represented by the following general formula (VIII) as a charge transporting material.
2. The electrophotographic photosensitive member according to item 1.・ General formula (VIII)

[0043]

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(In the above formula, R ₃₃ and R ₃₄ may be the same or different, and represent a hydrogen atom, an alkyl group, an alkoxy group,
Represents a halogen atom, and g and h each represent an integer of 1 or 2. R ₃₅ is a hydrogen atom, having 1 to 4 carbon atoms
Represents an alkyl group or an aryl group having 6 to 12 carbon atoms. )

( 12 ) The Bragg angle (2θ ± 2) of the X-ray diffraction spectrum using Cukα ray as the charge generation material
0.2 °), at least 7.4 °, 16.6 °
Electrophotography according to any one of inventions (8) to (11), wherein the photosensitive layer contains dichlorogallium phthalocyanine having diffraction peaks at the positions of °, 25.5 ° and 28.3 °. It is a photoconductor.

( 13 ) The Bragg angle (2θ ± 2) of the X-ray diffraction spectrum using Cukα ray as the charge generation material
0.2 °), at least 7.5 °, 9.9 °,
12.5 °, 16.3 °, 18.6 °, 25.1 °, 2
The electrophotographic photosensitive member according to any one of inventions (8) to (11), wherein the photosensitive layer contains hydroxygallium phthalocyanine having a diffraction peak at a position of 8.1 °.

( 14 ) The Bragg angle (2θ ±) of the X-ray diffraction spectrum using Cukα ray as the charge generating material
0.2 °), at least 9.5 °, 11.7
°, 15.0 °, 24.1 °, one of the invention, characterized in that the titanyl phthalocyanine having diffraction peaks at 27.3 ° contained in the photosensitive layer (8) - (11)
2. The electrophotographic photosensitive member according to item 1 .

[0048] (15) in an electrophotographic apparatus charging devices is a contact charging device, either INVENTION (1) - (14)
An electrophotographic apparatus using the electrophotographic photoreceptor according to claim 1 .

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. [Electrophotographic Photoreceptor] The electrophotographic photoreceptor of the present invention comprises a photosensitive layer on a conductive support.
In the electrophotographic photosensitive member provided, the photosensitive layer is a specific
It is characterized by containing a polycarbonate resin. Ma
The specific polycarbonate resin in the present invention
And will be described in detail. Specific polycarbonate resin in the Specific polycarbonate resin present invention, the terminal is characterized in that it has a hindered phenol structure or a hindered amine structure is the structure of the antioxidant, specifically, the following general formula (I). -General formula (I)

[0050]

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(In the above formula, at least one of the terminal groups of X ₁ and X ₂ represents a group selected from a group having a hindered phenol structure and a group having a hindered amine structure. Represents a necessary group, and p represents an integer capable of making the viscosity average molecular weight of the entire polycarbonate resin in a range of 3000 to 300,000. )

As described above, when the terminal of the polycarbonate resin has a hindered phenol structure or a hindered amine structure which is an antioxidant structure, a polycarbonate resin having an antioxidant function can be obtained. That is, when a hindered phenol structure or a hindered amine structure is copolymerized in a polycarbonate resin, these structures are eventually destroyed and the antioxidant function cannot be sufficiently exhibited.
As in the present invention, when the terminal has such a structure, the structure as an antioxidant is not impaired, and thus the antioxidant function can be sufficiently exhibited. A hindered phenol structure or a hindered amine structure which can be a terminal of a specific polycarbonate resin, that is, a group having a hindered phenol structure or a hindered amine structure which can be at least one of the terminal groups of X ₁ and X ₂ in the above general formula (I) Examples of the group having are as follows.

A hindered phenol structure represented by the following general formula (II): General formula (II)

[0054]

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(In the above formula, R ₁ and R ₈ each represent a branched alkyl group; R _{2 to} R ₇ each independently represent hydrogen, an alkyl group, an aryl group or an alkoxy group;
Represents an integer of 3, and Y ₁ is a linking group represented by the following structural formula .
Selected from

[0056]

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[0057] (In the above formula, R ₉ to R ₁₃ each independently represent a hydrogen, an alkyl group, an aryl group, an alkoxy group, a is an integer of 0.) Represented by) the formula (II) Specific examples of the hindered phenol structure are shown below. However, the present invention is not limited to the following specific examples.

[0058]

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Hindered phenol structure represented by the following general formula (III): General formula (III)

[0060]

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(In the above formula, at least one of R ₁₄ and R ₁₅ is a branched alkyl group, the rest is an alkyl group, an aryl group or an alkoxy group, and at least one of R ₁₆ and R ₁₇ is a branched alkyl group. And the rest represent an alkyl group, an aryl group or an alkoxy group, b and c each independently represent an integer of 1 to 3, m represents an integer of 1 to 3, and A represents -O- or -NH-. , Y ₂ represents a linking group or a single bond. ) Examples of the linking group for Y ₂ include the following.

[0062]

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Specific examples of the hindered phenol structure represented by the general formula (III) are shown below. However, the present invention is not limited to the following specific examples.

[0064]

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[0065]

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Hindered amine structure represented by the following general formula (IV): General formula (IV)

[0067]

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(In the above formula, at least one of Q _{1 to} Q ₃ is a group represented by the following structural formula;

[0069]

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The remainder is an alkyl group or the following structural formula

[0071]

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And Q ₄ represents hydrogen or an alkyl group having 1 to 13 carbon atoms. )

Specific examples of the hindered amine structure represented by the general formula (IV) are shown below. However, the present invention is not limited to the following specific examples.

[0074]

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[0075]

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Hindered amine structure represented by the following general formula (V): General formula (V)

[0077]

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(In the above formula, n represents an integer that allows the viscosity average molecular weight of the entire polycarbonate resin to fall within a range of 3000 to 300,000. )

The portion other than the terminal of the specific polycarbonate resin, that is, the polymerization unit, may be a polymerization unit of a conventionally known polycarbonate. For example, bisphenol (A), bisphenol (Z), bisphenol (C), bisphenol (TP), bisphenol (B
P) and other structural units of various polycarbonate resins. Particularly preferred polymerization units of the specific polycarbonate resin are those in which the R portion of the above general formula (I) is represented by a structural unit represented by the following general formula (VI).・ General formula (VI)

[0080]

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(In the above formula, R _{18 to} R ₂₁ each independently represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms,
5 alkoxy groups, and these groups may be substituted. Z represents a group represented by the following structural formula.

[0082]

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(In the above formula, R _{22 to} R ₂₉ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or R
₂₂ and R ₂₃ , R ₂₆ and R ₂₈ or R ₂₇ and R ₂₉ are bonded together to form a group forming a carbocyclic or heterocyclic ring, and these groups may be substituted. d represents 0 or 1. ))

Among these, a particularly preferred R moiety in the above general formula (I) is represented by the following structural formula.

[0085]

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Preferred specific examples of the polymerized unit containing R in the above formula (I) (the portion enclosed in parentheses in the formula (I)) are shown below, but the present invention is not limited thereto. .

[0087]

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[0088]

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[0089]

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The specific polycarbonate may be one in which only one of the above structural units is polymerized, or one in which two or more are copolymerized. In the case of copolymerization in the present invention, any polymerization method such as block, random, and graft polymerization methods can be used. By using a specific polycarbonate resin after copolymerization, it is possible to control properties according to the use and purpose. For example, compatibility with other resins, solubility in a solvent, film-forming properties, and the like can be adjusted. The molecular weight of the specific polycarbonate resin is appropriately selected depending on the application and required performance, but usually the viscosity average molecular weight is suitably in the range of 3000 to 300,000.

A specific polycarbonate resin can be produced by the following method. (1) Method using phosgene A specific polycarbonate resin can be produced by reacting the following compound A, which is an intermediate, with phosgene. The following compound A can be easily obtained from the market. -Compound A HO-R-OH In the formula, R represents a group necessary for constituting polycarbonate, and has the same meaning as R in the general formula (I). The reaction formula is as follows.

[0092]

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(2) Method Using Bischloroformate of Dihydroxy Compound The specific polycarbonate resin can be produced by reacting the compound A with the bischloroformate of dihydroxy compound. The reaction formula is as follows.

[0094]

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In the formula, R ′ has the same meaning as R in compound A, and R and R ′ may be the same or different.

(3) Method Using Monochloroformate of Dihydroxy Compound A specific polycarbonate resin can be produced by subjecting a monochloroformate of a dihydroxy compound to a self-condensation reaction. The reaction formula is as follows.

[0097]

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In the formula, R has the same meaning as R in compound A.

(4) Method Using Dialkyl Carbonate The specific polycarbonate resin can be produced by reacting the compound A with a dialkyl carbonate. The reaction formula is as follows.

[0100]

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In the formula, R ″ represents an alkyl group.

(5) Method Using Monocarbonate of Dihydroxy Compound The specific polycarbonate resin can be produced by subjecting a monocarbonate of a dihydroxy compound to a self-condensation reaction. The reaction formula is as follows.

[0103]

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In the formula, R has the same meaning as R in compound A. R ″ represents hydrogen, an alkyl group, or the like.

(6) Method Using Cyclic Polycarbonate A specific polycarbonate resin can be produced by subjecting a cyclic polycarbonate to a ring-opening polymerization reaction. The reaction formula is as follows.

[0106]

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In the formula, R has the same meaning as R in compound A.

(7) Method Using Carbon Dioxide and Cyclic Ether A specific polycarbonate resin can be produced by reacting carbon dioxide with a cyclic ether. The reaction formula is as follows.

[0109]

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In the formula, R has the same meaning as R in compound A.

(8) Method Using Carbonate and Dihalide A specific polycarbonate resin can be produced by reacting a carbonate with a dihalide. The reaction formula is as follows.

[0112]

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In the formula, R has the same meaning as R in compound A. M represents a monovalent metal atom, NH ₄ or the like. X represents a halogen atom.

[0114] The above-mentioned method can be mentioned as a method for producing a specific polycarbonate resin. In general, the most widely used method for producing a polycarbonate resin is as follows.
This is a method using (1) phosgene.

In the production of a specific polycarbonate resin, as a method for modifying the terminal to a group having a hindered phenol structure or a group having a hindered amine structure, for example, an intermediate having a bisphenol structure (compound A) and phosgene are used. In the method (1) for synthesizing a polycarbonate resin by reacting, the reaction can be carried out by adding a compound selected from hindered phenol and hindered amine as a polymerization terminator at the end of the polymerization. Can be synthesized. Specific examples of the compound of hindered phenol and hindered amine include compounds in which a hydroxyl group is bonded to a bond part in the specific examples of the group having a hindered phenol structure or the group having a hindered amine structure.

Next, a specific synthesis example of a specific polycarbonate resin will be described. Synthesis Example (Synthesis of Polycarbonate Resin Having Structural Formula 2-1 at Terminal of Polymerized Unit Represented by Structural Formula 4-8) 0.2 mol of a bisphenol compound having the following structure in a 2 liter reactor,
400 ml of a 4.7% strength aqueous sodium hydroxide solution and 350 ml of methylene chloride were added, and phosgene was blown in at a rate of 400 ml / min for 15 minutes with vigorous stirring.

[0117]

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The reaction temperature was kept at 15 ° C., and 13.7%
40 ml of sodium hydroxide, 0.2 g of trimethylbenzylammonium chloride and 0.3 ml of triethylamine were added, and the mixture was stirred at 23 ° C. to carry out a polycondensation reaction. After about one hour, 0.003 mol of a hindered phenol compound having the following structure was added to terminate the polycondensation reaction.

[0119]

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After completion of the reaction, the product was treated with methylene chloride 400
diluted with water, 1 liter of water, 0.01N hydrochloric acid.
Washed sequentially with 5 liters and 1 liter of water. The obtained organic phase was poured into 5 liters of methyl alcohol to precipitate a white polymer, which was separated by filtration and dried at 100 ° C. for 12 hours.
About 17 g of a polycarbonate resin having the structural formula 2-1 at the terminal of the polymerization unit represented by the structural formula 4-8 was obtained.

An example of the constitution of the electrophotographic photosensitive member of the present invention using the above specific polycarbonate resin will be described. <Support> In the electrophotographic photoreceptor of the present invention, as the conductive support, metal drums and sheets of aluminum, copper, iron, zinc or nickel; aluminum, copper, gold, paper, plastic or glass; A metal such as silver, platinum, palladium, titanium, nickel-chromium, stainless steel or copper-indium is deposited or indium oxide,
Evaporating a conductive metal compound such as tin oxide, laminating a metal foil, or dispersing carbon black, indium oxide, tin oxide-antimony oxide powder, metal powder or copper iodide in a binder resin and applying As a result, a known material such as a drum-shaped, sheet-shaped or plate-shaped material subjected to a conductive treatment can be used. When using a metal pipe base material as a metal drum, even if the surface remains a raw tube, mirror cutting, etching, anodic oxidation, rough cutting,
Processing such as centerless grinding, sand blasting, and wet honing may be performed. By roughening the surface of the base material by the surface treatment, it is possible to prevent grain-like density unevenness due to interference light in the photoconductor, which may occur when a coherent light source such as a laser beam is used.

<Undercoat Layer> The undercoat layer is formed of an acetal resin such as polyvinyl butyral, a polyvinyl alcohol resin, casein, a polyamide resin, a cellulose resin, gelatin, a polyurethane resin,
Polymer resin compounds such as polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, and melamine resin Besides, zirconium, titanium, aluminum,
Examples include organometallic compounds containing manganese, silicon atoms, and the like. These compounds can be used alone or as a mixture or a polycondensate of a plurality of compounds. Among them, organometallic compounds containing zirconium or silicon are excellent in performance, such as low residual potential, small potential change due to environment, and small potential change due to repeated use.

Examples of the silicon compound include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N- β- (aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β
-Hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, particularly preferred silicon compounds are vinyltriethoxysilane, vinyltris (2-methoxyethoxysilane), 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, N-2-
(Aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- Silane coupling agents such as mercaptopropyltrimethoxysilane and 3-chloropropyltrimethoxysilane are exemplified.

Examples of the organic zirconium compound include zirconium butoxide, ethyl zirconium acetoacetate,
Zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, Examples include methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide, and the like.

Examples of the organic titanium compound include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate Examples thereof include ammonium salts, titanium lactate, titanium lactate ethyl ester, titanium triethanolamine, and polyhydroxytitanium stearate. Examples of the organic aluminum compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethylacetoacetate aluminum diisopropylate, and aluminum tris (ethylacetoacetate).

Various organic or inorganic fine powders can be mixed in the undercoat layer for the purpose of improving electric characteristics and light scattering. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white, and lithopone; inorganic pigments such as alumina, calcium carbonate, and barium sulfate; and Teflon resin particles, benzoguanamine resin particles, and styrene resin particles Etc. are effective. The particle size of the added fine powder is 0.01 to 2 μm. The thickness of the undercoat layer is preferably in the range of 0.1 to 10 μm. The fine powder is added as needed, but when added, it is added in an amount of 10 to 80% by weight, more preferably 30 to 70% by weight, based on the solid content of the undercoat layer. In the formation of the undercoat layer coating liquid, when the added fine powder is mixed, it is added to a solution in which a resin component is dissolved to perform a dispersion treatment. As a method of dispersing the added fine powder in the resin, a method such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used.

<Photosensitive Layer> The photosensitive layer formed on the undercoat layer may have a single-layer structure or a laminated structure in which a charge generation layer and a charge transport layer are functionally separated. Is also good. Further, a surface protective layer can be formed on these photosensitive layers as needed. FIG. 1 is a cross-sectional view showing an example of an electrophotographic photosensitive member in the case of a photosensitive layer having a laminated structure. Reference numeral 11 denotes a conductive support, and 12 denotes an undercoat layer. These components are as described above. Reference numeral 13 denotes a charge generation layer, and further a charge transport layer 1
4 is provided thereon. However, in the case of a stacked structure, the charge generation layer and the charge transport layer may be stacked in any order. By using the above-mentioned specific polycarbonate resin for both or one of the charge generation layer and the charge transport layer as the binder resin, the mechanical strength is high, the surface deterioration due to oxidation is reduced, and the stability in repeated use is improved. The electrophotographic photoreceptor of the present invention having excellent properties can be produced.
In the case of a single-layer structure, the charge generation material and the charge transport material described below are contained in one layer, and a specific polycarbonate resin is formed as a binder resin. , And stability at the time of repeated use can be realized by reducing surface deterioration due to oxidation.

1. First, the case of a photosensitive layer having a laminated structure will be described. (Charge Generating Layer) The charge generating layer is formed by forming a charge generating substance by vacuum evaporation or by dispersing and applying the charge generating substance together with an organic solvent and a binder resin. As the charge generating material, amorphous selenium, crystalline selenium, selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, zinc oxide, inorganic photoconductors such as titanium oxide, metal-free phthalocyanine, Titanyl phthalocyanine, copper phthalocyanine,
Various phthalocyanine pigments such as tin phthalocyanine and gallium phthalocyanine, and various organic pigments and dyes such as squarium-based, anthantrone-based, perylene-based, azo-based, anthraquinone-based, pyrene-based, pyrylium salts, and thiapyrylium salts are used. In addition, these organic pigments generally have several types of crystal forms.In particular, phthalocyanine pigments are known to have various crystal types such as α-type and β-type. Any of these crystal forms can be used as long as the pigment is obtained.

In connection with a specific polycarbonate resin contained in both or one of the charge generation layer and the charge transport layer, the sensitivity is high for adaptation to a high-speed electrophotographic apparatus requiring high durability. The following compounds may be mentioned as charge generation materials that provide excellent performance in the sense. 1) At least 7.4 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray.
Dichlorogallium phthalocyanine having diffraction peaks at positions of °, 16.6 °, 25.5 ° and 28.3 °. 2) At least 7.5 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cuka radiation.
°, 9.9 °, 12.5 °, 16.3 °, 18.6 °,
Hydroxygallium phthalocyanine having diffraction peaks at 25.1 ° and 28.1 °. 3) At least 9.5 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray.
°, 11.7 °, 15.0 °, 24.1 °, 27.3 °
Titanyl phthalocyanine having a diffraction peak at the position.

[0130] As in the binder resin in the charge generating layer, especially
Specific polycarbonate resins or the following can be exemplified. That is, polycarbonate resin such as bisphenol A type or bisphenol Z type, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer Coalescing resin,
Vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-
N-vinyl carbazole and the like. These binder resins can be used alone or in combination of two or more. Compounding ratio of charge generation material and binder resin (weight ratio)
Is preferably in the range of 10: 1 to 1:10. Further, the thickness of the charge generation layer is generally set in the range of 0.01 to 5 μm, preferably 0.05 to 2.0 μm. As a method of dispersing the charge generating material in the resin, a roll mill,
Methods such as a ball mill, a vibrating ball mill, an attritor, a dyno mill, a sand mill, and a colloid mill can be used.

(Charge Transport Layer) The charge transport layer comprises at least a charge transport material and a binder resin. Examples of the charge transport material used in the charge transport layer include the following. 2,5-bis (p-
Oxadiazole derivatives such as diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [pyridyl- (2)]-3
Pyrazoline derivatives such as-(p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, triphenylamine, tri (P-methyl) phenylamine, N, N-bis (3,4-dimethylphenyl) biphenyl- 4-amine, dibenzylaniline, 9,9-
Dimethyl-N, N-di (p-tolyl) fluorenone-2
-Aromatic tertiary amino compounds such as amines, N, N'-
Diphenyl-N, N'-bis (3-methylphenyl)-
Aromatic tertiary diamino compounds such as [1,1-biphenyl] -4,4'-diamine, 3- (4'dimethylaminophenyl) -5,6-di- (4'-methoxyphenyl)
1,2,4-triazine derivatives such as -1,2,4-triazine, 4-diethylaminobenzaldehyde-1,
1-diphenylhydrazone, 4-diphenylaminobenzaldehyde-1,1-diphenylhydrazone, [p-
Hydrazone derivatives such as (diethylamino) phenyl] (1-naphthyl) phenylhydrazone, 2-phenyl-
Quinazoline derivatives such as 4-styryl-quinazoline, 6
-Hydroxy-2,3-di (p-methoxyphenyl)-
Benzofuran derivatives such as benzofuran, p- (2,2
Α-stilbene derivatives such as -diphenylvinyl) -N, N-diphenylaniline, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, poly-N-
Hole transport materials such as vinyl carbazole and its derivatives. Chloranyl, bromoanil, quinone compounds such as anthraquinone, tetracyanoquinodimethane compounds,
2,4,7-trinitrofluorenone, 2,4,5,7
Fluorenone compounds such as -tetranitro-9-fluorenone, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole and 2,5-
Bis (4-naphthyl) -1,3,4-oxadiazole, 2,5-bis (4-diethylaminophenyl) 1,
Oxadiazole compounds such as 3,4 oxadiazole, xanthone compounds, thiophene compounds,
An electron transporting substance such as a diphenoquinone compound such as 3 ', 5,5'tetra-t-butyldiphenoquinone; Alternatively, a polymer having a group consisting of the compounds shown above in a main chain or a side chain may be used. These charge transport materials are:
Species or a combination of two or more can be used.

In the case of a laminated photoreceptor, the charge polarity of the photoreceptor varies depending on the charge transport polarity of the charge transport material. When a hole transport material is used, the photoreceptor is used with negative charge, and when an electron transport material is used, the photoreceptor is used with positive charge. When both are mixed, a photoreceptor having both charging polarities is possible.

[0133] When the specific polycarbonate resin in the charge transport layer was used as the binder resin, in connection with a specific polycarbonate resin, the following compounds as a charge-transporting material compatibility particularly excellent performance is good can be obtained Is mentioned. 1) Benzidine compounds represented by the following general formula (VII)-General formula (VII)

[0134]

Embedded image

(In the above formula, R ₃₀ and R ₃₀ ′ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, and R ₃₁ , R ₃₁ ′, R ₃₂ and R ₃₂ 'May be the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group, and e, e', f, and f 'each independently represent an integer of 1 or 2. ) This general formula (VI
Table 1 shows specific examples of the benzidine compound represented by I).

[0136]

[Table 1]

[0137]

[Table 2]

[0138]

[Table 3]

2) Triarylamine compounds represented by the following general formula (VIII): General formula (VIII)

[0140]

Embedded image

(In the above formula, R ₃₃ and R ₃₄ may be the same or different, and represent a hydrogen atom, an alkyl group, an alkoxy group,
Represents a halogen atom, and g and h each represent an integer of 1 or 2. R ₃₅ is a hydrogen atom, having 1 to 4 carbon atoms
Represents an alkyl group or an aryl group having 6 to 12 carbon atoms. ) Shows a specific compound examples of the triarylamine compound represented by the general formula (VIII) in Table 2 below.

[0142]

[Table 4]

[0143]

[Table 5]

In the present invention, as the binder resin of the charge transporting material, a specific polycarbonate resin or other resins mentioned as the binder resin of the charge generating material are used. Special
Certain polycarbonate resins can be used by mixing or copolymerizing with other resins for the purpose of improving the compatibility of the charge transporting material, improving the solubility in a solvent, and improving the film forming property.
Examples of resins that can be used as a mixture or copolymerized are different polycarbonate resins in the general formula (I), bisphenol (A), bisphenol (Z),
Various polycarbonate resins using bisphenol (C), bisphenol (TP), bisphenol (BP), etc., polyester resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinyl acetate resins, styrene-butadiene copolymer resins , Vinylidene chloride-acrylonitrile copolymer resin,
Vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-
Formaldehyde resin, styrene-alkyd resin, poly-N-vinyl carbazole and the like can be mentioned.

In the case of copolymerization in the present invention,
Any polymerization method such as block, random, and graft polymerization methods can be used. In the case of copolymerization, the proportion of the structural unit represented by the general formula (I) is 5 to 90.
% Is preferable, and the copolymerization effect is particularly exhibited by a ratio of 10 to 90%. When a specific polycarbonate resin and another resin are mixed and used, the mixing ratio of the other resin is preferably 5 to 70% of the total resin components. The molecular weight of the specific polycarbonate resin used for the charge transport layer is appropriately selected depending on film forming conditions such as the thickness of the photosensitive layer and a solvent, or mechanical properties such as desired abrasion resistance, but usually the viscosity average molecular weight The range is preferably from 3000 to 300,000, more preferably from 20,000 to 200,000.

The charge transport layer can be formed by applying and drying a solution in which the above-described charge transport material and the binder resin are dissolved in a suitable solvent. Examples of the solvent used for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, and chlorobenzene; ketones such as acetone and 2-butanone; and halogenated compounds such as methylene chloride, chloroform, and ethylene chloride. Aliphatic hydrocarbons, cyclic or linear ethers such as tetrahydrofuran, dioxane, ethylene glycol, and diethyl ether, or a mixed solvent thereof can be used. The compounding ratio of the charge transport material and the binder resin is 10: 1.
１ ： 1: 5 is preferred. The thickness of the charge transport layer is generally 5
It is set in the range of 50 to 50 m, preferably 10 to 40 m, and more preferably 10 to 30 m.

With respect to ozone, oxidizing gas or heat generated in the electrophotographic apparatus, the deterioration of the photoreceptor can be prevented by the hindered phenol structure or hindered amine structure at the terminal of the polycarbonate resin, but more effective. In order to prevent deterioration of the photoconductor, additives such as an antioxidant and an ultraviolet absorber can be added to the charge transport layer. For example, organic sulfur-based and organic phosphorus-based antioxidants are called secondary antioxidants. If the hindered phenol structure or hindered amine structure at the end of a specific polycarbonate resin is used as the primary antioxidant, the secondary antioxidant is used. A synergistic effect can be obtained by using the agent in combination.

Examples of the ultraviolet absorber include benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine derivatives. 2-hydroxy-4 as a benzophenone-based ultraviolet absorber
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-di-hydroxy-4
-Methoxybenzophenone and the like. 2-(-2'-hydroxy-5'methylphenyl-)-benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4",
5 ", 6" -tetra-hydrophthalimido-methyl)-
5'-methylphenyl] -benzotriazole, 2-
(-2'-hydroxy-3'-t-butyl-5'-methylphenyl-)-5-chlorobenzotriazole, 2-
(2′-hydroxy-3′-tert-butyl 5′-methylphenyl-)-5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-t-butylphenyl-)-benzotriazole, 2- (2′-hydroxy-
5′-t-octylphenyl) -benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl-)-benzotriazole and the like.
Other compounds include 2,4, di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, nickel dibutyl-dithiocarbamate and the like.

Further, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue when repeatedly used. Examples of the electron-accepting substance that can be used in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and o. -Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like. Of these, fluorenone-based, quinone-based, and benzene derivatives having an electron-withdrawing substituent such as Cl, CN, and NO ₂ are particularly preferable.

The charge transport layer can be formed by applying a solution obtained by dissolving the above-described charge transport material and a specific polycarbonate resin in an appropriate solvent, and drying the solution. Typical solvents used for forming the charge transport layer include, for example, benzene, toluene,
Aromatic hydrocarbons such as chlorobenzene, acetone, 2-
Ketones such as butanone, methylene chloride, chloroform,
Halogenated aliphatic hydrocarbons such as ethylene chloride, cyclic or linear ethers such as tetrahydrofuran, dioxane, ethylene glycol, diethyl ether and the like, or a mixed solvent thereof can be used. A small amount of silicone oil can be added to the coating solution as a leveling agent for improving the smoothness of the coating film.

The coating can be performed by a coating method such as a dip coating method, a ring coating method, a spray coating method, a bead coating method, a blade coating method, and a roller coating method, depending on the shape and application of the photoreceptor. . Drying is preferably performed by heat drying after touch drying at room temperature. Heat drying is 30 ℃ ～ 2
It is desirable to carry out at a temperature of 00 ° C. for a time in the range of 5 minutes to 2 hours.

2. Single-layered photosensitive layer When the photosensitive layer has a single-layered structure, the photosensitive layer is coated with a solution prepared by dissolving the aforementioned charge generation material, charge transport material, and a specific polycarbonate resin as a binder resin in an appropriate solvent, and dried. Can be formed. Solvents that can be used are the same as those described in the production of the charge transport layer. In addition, additives such as an antioxidant, a light stabilizer, a heat stabilizer, an electron-accepting material, and silicone oil can be added to the photosensitive layer in the same manner as described in the production of the charge transport layer. The method is the same as the method described in the production of the charge transport layer. The mixing ratio of the charge transport material to the specific polycarbonate resin is preferably from 1: 3 to 6: 4. The mixing ratio of the charge generating material to the specific polycarbonate resin is preferably from 1: 1 to 1:10. When the specific polycarbonate resin is small, the mechanical strength is weak,
If too large, the sensitivity and the light decay rate decrease. The thickness of the photosensitive layer is generally 5 to 50 μm, preferably 10 to 30 μm.
Is set in the range.

<Surface Protective Layer> A surface protective layer can be formed on the photosensitive layer if necessary. As the surface protective layer, there is an insulating resin protective layer or a low resistance protective layer in which a resistance adjuster is added to the insulating resin. In the case of a low resistance protective layer, for example, a layer in which conductive fine particles are dispersed in an insulating resin can be used. The number average particle diameter (D ₅₀ ) of white, gray or bluish white having an electric resistance of 10 ⁹ Ω · cm or less as conductive fine particles is 0.3.
μm or less, more preferably 0.1 μm or less fine particles, for example, molybdenum oxide, tungsten oxide, antimony oxide, tin oxide, titanium oxide, indium oxide, a solid solution carrier of tin oxide and antimony or antimony oxide or A mixture of these, or a mixture of these metal oxides in a single particle, or a coating of these particles is given. Above all, tin oxide or a solid solution of tin oxide and antimony or antimony oxide is preferably used because the electrical resistance can be appropriately adjusted and the protective layer can be made substantially transparent ( JP-A-57-30847, JP-Sho 57-12
See JP-A-8344).

Examples of the insulating resin include condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, and polyacrylamide .

[Electrophotographic Apparatus] The electrophotographic photoreceptor of the present invention using the specific polycarbonate resin produced as described above is a light lens type copier, a laser beam emitting near-infrared light or visible light. It can be used in electrophotographic devices such as printers, digital copiers, LED printers, and laser facsimile machines. The electrophotographic photoreceptor of the present invention can be used in combination with a one-component or two-component regular developer or a reversal developer. Further, the electrophotographic photoreceptor of the present invention can obtain good characteristics with less occurrence of current leak even in a contact charging type electrophotographic apparatus using a charging roller or a charging brush.

FIG. 2 is a schematic sectional view showing an example of a contact charging type electrophotographic apparatus using a charging roller. FIG.
In, 21 denotes an electrophotographic photosensitive member, the surface Patent
The photosensitive layer has a fixed polycarbonate resin as a binder resin. The electrophotographic photosensitive member 21 is driven to rotate in the direction of the arrow by a driving unit (not shown). Around the electrophotographic photosensitive member 21, along a rotation direction thereof, a contact charging device 22 using a charging roller, an exposing unit 23, and a developing device 2 having a developer carrier facing the electrophotographic photosensitive member 21.
4, a transfer corotron 25, a cleaner 26, and a light neutralizer 27 are sequentially arranged.

First, the surface of the electrophotographic photosensitive member 21 is uniformly charged by the contact charging device 22. Subsequently, the image portion is exposed by the exposure means 3 to form a latent image, and the latent image is developed by the developing device 24 with toner and visualized. Subsequently, the toner image formed on the electrophotographic photosensitive member 21 is transferred onto the recording paper 28 by charging the transfer corotron 25. Thereafter, the recording sheet 28 is conveyed to the fixing device 29, and the toner image is fixed on the recording sheet 28, and a series of image recording steps is completed. After the transfer of the toner image is completed, the surface of the electrophotographic photoreceptor 21 is cleaned by a cleaner 26 to remove residual toner, and then exposed to light by a photo-static eliminator 27 to remove residual charges, thereby preparing for the next image recording step. .

[0158]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 n-butyl alcohol 17 in which 4 parts by weight of a polyvinyl butyral resin (S-LEC BM-S manufactured by Sekisui Chemical) was dissolved
0 parts by weight, 30 parts by weight of an organic zirconium compound (acetylacetone zirconium butyrate) and 3 parts by weight of a mixture of organic silane compounds (γ-aminopropyltrimethoxysilane) were additionally mixed and stirred to obtain a coating liquid for an undercoat layer. The center line average roughness Ra is obtained by performing liquid honing using a spherical alumina fine powder having a D50 of 30 μm.
An undercoat layer is applied using a dip coater on a 30 mmφ ED tube aluminum substrate roughened to 0.18 μm, and cured at 150 ° C. for 1 hour to give a film thickness of 1.2 μm.
m was formed. 7.4 as charge generation material
3 parts by weight of dichlorogallium phthalocyanine having clear X-ray diffraction peaks at positions of °, 16.6 °, 25.5 ° and 28.3 °, and 2 parts by weight of vinyl chloride / vinyl acetate copolymer resin (Nihon Unicar VMCH) And a mixture consisting of 180 parts by weight of butyl acetate were dispersed in a sand mill for 4 hours. This liquid was applied onto the undercoat layer by dip coating and dried to form a film having a thickness of 0.1 mm.
A 2 μm charge generation layer was formed. Next, Compound No. 5-
The N, N'-diphenyl-N, N'-bis (3-
Methylphenyl)-[1,1′-biphenyl] -4,
4′-diamine (4 parts by weight) and structural formula 4 as a binder resin
-6 and 6 parts by weight of a resin having a structural formula 2-1 at the terminal of polycarbonate (molecular weight: about 40,000)
0 parts by weight were added and dissolved. Using this solution, apply 1
By performing drying at 20 ° C. for 40 minutes, a charge transport layer having a thickness of 25 μm was formed, and an electrophotographic photosensitive member having three layers was manufactured. The obtained electrophotographic photosensitive member was mounted on a printer (LP-9100: manufactured by EPSON) using a contact charging system to perform a printing operation. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. The results obtained are shown in Table 4 below.

Examples 2 to 11 An undercoat layer and a charge generation layer were formed in the same manner as in Example 1 on a base material obtained in the same manner as in Example 1, and the charge transport layer was used as a binder resin. The charge transport layer was formed in the same manner as in Example 1 except that the polycarbonate resin having a hindered phenol structure at the end was used as shown in Table 3, to prepare an electrophotographic photosensitive member having three layers.

[0160]

[Table 6]

The obtained electrophotographic photosensitive member was transferred to a printer (LP-9100: EP) having a contact charging type charging device.
SON) and a printing operation was performed. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 4 shows the obtained results.

Comparative Example 1 An undercoat layer and a charge generation layer were formed on a substrate obtained in the same manner as in Example 1 in the same manner as in Example 1. On top of this, N, N'-diphenyl-N, N 'shown in Compound No. 5-1
-Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (4 parts by weight) and a polycarbonate resin represented by the structural formula 4-8 as a binder resin (with no terminal modification, a molecular weight of about (40,000) and 6 parts by weight were dissolved by adding 80 parts by weight of tetrahydrofuran. Using this solution, apply and dry at 120 ° C. for 40 minutes to obtain a film thickness of 25 μm.
Was formed to prepare an electrophotographic photosensitive member having three layers. The obtained electrophotographic photosensitive member was converted to a printer (LP-9100: EPS) having a contact charging type charging device.
ON made) and a print operation was performed. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 4 shows the obtained results.

Comparative Example 2 An undercoat layer and a charge generation layer were formed on a substrate obtained in the same manner as in Example 1 in the same manner as in Example 1. On top of this, N, N'-diphenyl-N, N 'shown in Compound No. 5-1
-Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (4 parts by weight) and a polycarbonate resin represented by the structural formula 4-8 as a binder resin (with no terminal modification, a molecular weight of about (40,000) 6 parts by weight and 2,6-di-t-butyl-4-methylphenol 0.2 part by weight were dissolved by adding 80 parts by weight of tetrahydrofuran. Using this solution, coating was performed and drying was performed at 120 ° C. for 40 minutes to form a charge transport layer having a thickness of 25 μm, thereby producing an electrophotographic photoreceptor having three layers. A printer (LP-910) having a charging device of a contact charging system was used for the obtained electrophotographic photosensitive member.
0: manufactured by EPSON) and a printing operation was performed.
At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 4 shows the obtained results.

[0164]

[Table 7]

Examples 12 to 18 On the base material obtained in the same manner as in Example 1, an undercoat layer and a charge generation layer were formed in the same manner as in Example 1, and the charge transport layer was used as a binder resin. A charge transport layer was formed in the same manner as in Example 1 except that the resins shown in Table 5 were used as the polycarbonate resins having a hindered phenol structure at the terminal, respectively, to produce an electrophotographic photosensitive member having three layers.

[0166]

[Table 8]

The obtained electrophotographic photosensitive member was transferred to a printer (LP-9100: EP) having a contact charging type charging device.
SON) and a printing operation was performed. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.

Comparative Examples 3 to 9 On the base material obtained in the same manner as in Example 1, an undercoat layer and a charge generation layer were formed in the same manner as in Example 1. In the charge transport layer, a polycarbonate resin as a binder resin is shown in Table 5 (resin not modified, molecular weight of about 40,000).
A charge transporting layer was formed in the same manner as in Example 1 except for using, and an electrophotographic photosensitive member having three layers was produced. The obtained electrophotographic photoreceptor was mounted on a printer (LP-9100: manufactured by EPSON) having a charging device of a contact charging system to perform a printing operation. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.

Example 19 An undercoat layer and a charge generation layer were formed on a substrate obtained in the same manner as in Example 1 by the same method as in Example 1. In the charge transport layer, Compound No. was used as a charge transport agent. A three-layered electrophotographic photoreceptor in which a charge transport layer is formed in the same manner as in Example 1 except that N, N-bis (3,4-dimethylphenyl) biphenyl-4-amine shown by 6-33 is used. Was prepared. The obtained electrophotographic photosensitive member was converted to a printer (LP-9100: EPSON) having a contact charging type charging device.
) And a printing operation was performed. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.
Shown in

Comparative Example 10 An undercoat layer and a charge generation layer were formed on a substrate obtained in the same manner as in Example 1 in the same manner as in Example 1. In the charge transport layer, the charge transport layer was formed in the same manner as in Comparative Example 1 except that N, N-bis (3,4-dimethylphenyl) biphenyl-4-amine represented by Compound No. 6-33 was used as the charge transport agent. Thus, an electrophotographic photosensitive member having three layers was prepared. The obtained electrophotographic photosensitive member was converted to a printer (LP-9100: EPSON) having a contact charging type charging device.
) And a printing operation was performed. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.
Shown in

Example 20 An undercoat layer and a charge generation layer were formed on a substrate obtained in the same manner as in Example 1 in the same manner as in Example 1. 7.5 °, 9.9 °, 12.5 °, 16.3 as charge generation material
9 parts by weight of hydroxygallium phthalocyanine having diffraction peaks at positions of °, 18.6 °, 25.1 °, and 28.1 °, 2 parts by weight of polyvinyl butyral resin (Eslec BM-1 manufactured by Sekisui Chemical), n-butyl alcohol The mixture consisting of 30 parts by weight was placed in a ball mill pot, milled for 60 hours by using a 1 / 8-inch φ SUS ball as a mill member, and further diluted with 30 parts by weight of n-butyl alcohol and stirred and stirred. The composition was applied on the undercoat layer and dried to form a charge generation layer having a thickness of 0.3 μm. The charge transport layer was formed in the same manner as in Example 1 to prepare an electrophotographic photoreceptor having three layers. The obtained electrophotographic photoreceptor was mounted on a printer (LP-9100: manufactured by EPSON) having a charging device of a contact charging system to perform a printing operation. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.

Comparative Example 11 An undercoat layer was formed in the same manner as in Example 1 on a substrate obtained in the same manner as in Example 1. 6. As a charge generation material
5 °, 9.9 °, 12.5 °, 16.3 °, 18.6
9 parts by weight of hydroxygallium phthalocyanine having diffraction peaks at positions of °, 25.1 ° and 28.1 °, polyvinyl butyral resin (Eslec BM-1 manufactured by Sekisui Chemical)
A mixture consisting of 2 parts by weight and 30 parts by weight of n-butyl alcohol was placed in a ball mill pot and milled for 60 hours using a 1/8 inch φ SUS ball as a mill member, and then 30 parts by weight of n-butyl alcohol was added. The diluted and stirred liquid was applied on the undercoat layer and dried to form a 0.3 μm-thick charge generation layer. The charge transport layer was formed in the same manner as in Comparative Example 1 to produce an electrophotographic photoreceptor having three layers. A printer (LP-910) having a charging device of a contact charging system was used for the obtained electrophotographic photosensitive member.
0: manufactured by EPSON) and a printing operation was performed.
At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.

Example 21 An undercoat layer and a charge generation layer were formed in the same manner as in Example 1 on a substrate obtained in the same manner as in Example 1. 9.5 °, 11.7 °, 15.0 °, 24.1 as charge generation material
A mixture consisting of 15 parts by weight of titanyl phthalocyanine having a clear X-ray diffraction peak at the positions of ° and 27.3 °, 10 parts by weight of a polyvinyl butyral resin (ESREC BM-S manufactured by Sekisui Chemical), and 300 parts by weight of n-butyl alcohol. The mixture was dispersed in a sand grind mill for 4 hours. This liquid was applied on the undercoat layer and dried to form a 0.2 μm-thick charge generation layer. The charge transport layer was formed in the same manner as in Example 1 to prepare an electrophotographic photoreceptor having three layers. The obtained electrophotographic photoreceptor was mounted on a printer (LP-9100: manufactured by EPSON) having a charging device of a contact charging system to perform a printing operation. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.

Comparative Example 12 An undercoat layer was formed on a substrate obtained in the same manner as in Example 1 by the same method as in Example 1. 9.5 as charge generation material
°, 11.7 °, 15.0 °, 24.1 °, 27.3 °
A mixture consisting of 15 parts by weight of titanyl phthalocyanine having a clear X-ray diffraction peak at the position, 10 parts by weight of a polyvinyl butyral resin (S-LEC BM-S manufactured by Sekisui Chemical), and 300 parts by weight of n-butyl alcohol was mixed with a sand grind mill. Time dispersed. This liquid was applied on the undercoat layer and dried to form a 0.2 μm-thick charge generation layer. The charge transport layer was formed in the same manner as in Comparative Example 1 to produce an electrophotographic photosensitive member having three layers. The obtained electrophotographic photoreceptor was mounted on a printer (LP-9100: manufactured by EPSON) having a charging device of a contact charging system to perform a printing operation. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 6 shows the obtained results.

[0175]

[Table 9]

Example 22 As a charge generation material, 7.4 °, 16.6 °, 25.5
1 part by weight of dichlorogallium phthalocyanine having a clear X-ray diffraction peak at the positions of ° and 28.3 °, and a resin having the structural formula 2-1 at the terminal of the polycarbonate represented by the structural formula 4-8 as a binder resin (Molecular weight of about 40,000) and 5 parts by weight of a tetrahydrofuran solution were combined with the charge transporting material N, N′-diphenyl-N,
N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine 1 part by weight, 2,6-dimethyl-2 ', 6'-di-t-butyl-4, After dispersing using a ball mill together with 1 part by weight of 4'-diphenoquinone, 300 parts by weight of tetrahydrofuran was newly added, and the center line average roughness Ra = 0.18 by a ring coating method.
It was applied on an 84 mmφ ED tube aluminum substrate roughened to a thickness of μm and dried at 100 ° C. for 60 minutes.
An electrophotographic photosensitive member having a single-layer structure of 5 μm was prepared. The obtained electrophotographic photoreceptor was mounted on a printer (LP-9100: manufactured by EPSON) having a charging device of a contact charging system to perform a printing operation. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 7 shows the obtained results.

Comparative Example 13 The procedure of Example 22 was repeated, except that the binder resin was changed to a polycarbonate resin represented by Structural Formula 4-8 (no terminal modification, molecular weight of about 40,000). An electrophotographic photosensitive member having a single layer structure was produced. The obtained electrophotographic photoreceptor was mounted on a printer (LP-9100: manufactured by EPSON) having a charging device of a contact charging system to perform a printing operation. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 7 shows the obtained results.

[0178]

[Table 10]

Examples 23 and 24 An undercoat layer and a charge generation layer were formed on a substrate obtained in the same manner as in Example 1 in the same manner as in Example 1, and the charge transport layer was used as a binder resin. A charge transport layer was formed in the same manner as in Example 1, except that a polycarbonate resin having a hindered amine structure at each terminal shown in Table 8 was used.
An electrophotographic photosensitive member having three layers was produced.

[0180]

[Table 11]

[0181]

Embedded image

The obtained electrophotographic photosensitive member was transferred to a printer (LP-9100: EP) having a charging device of a contact charging system.
SON) and a printing operation was performed. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 9 shows the obtained results.

[0183]

[Table 12]

Comparative Example 14 An undercoat layer and a charge generation layer were formed on a base material obtained in the same manner as in Example 1 by the same method as in Example 1, and the binder resin was replaced with a structural formula in the charge transport layer. 4-8 and a polycarbonate resin (with no terminal modification, molecular weight of about 40,000) which is a random copolymer (copolymerization ratio 9: 1) comprising both structural units of the following structural formula (hindered phenol structure) Then, a charge transport layer was formed in the same manner as in Example 1 to prepare an electrophotographic photosensitive member having three layers.

[0185]

Embedded image

The obtained electrophotographic photosensitive member was transferred to a printer (LP-9100: EP) having a charging device of a contact charging system.
SON) and a printing operation was performed. At that time, the residual potential and the image quality of the photoconductor were evaluated. After performing a print test of 50,000 sheets, the image quality was examined. Table 10 shows the obtained results.

[0187]

[Table 13]

[0188]

According to the present invention, in order to have a hindered phenol structure or a hindered amine structure in its end, usefulness polycarbonate resin having excellent anti-oxidation function
And because of the use in the photosensitive layer of the electronic photosensitive member, the formed photosensitive layer has excellent characteristics also electric properties and image quality in repeated use. Therefore, the electrophotographic photoreceptor of the present invention has high durability, and by using the electrophotographic photoreceptor of the present invention, highly stable image quality can be obtained for a long period of time.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of the surface of an electrophotographic photosensitive member having a laminated structure, which is an example of the electrophotographic photosensitive member of the present invention.

FIG. 2 is a schematic sectional view of an electrophotographic apparatus suitable for applying the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 11: conductive support 12: undercoat layer 13: charge generation layer 14: charge transport layer 21: electrophotographic photosensitive member 22: contact charging device 23: exposure means 24: developing device 25: transfer corotron 26: cleaner 27: light Static eliminator 28: Recording paper 29: Fixer

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Ichiro Takekawa 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd. (56) References JP-A-8-253575 (JP, A) JP-A-2-132452 ( JP, A) JP-A-9-157379 (JP, A) JP-A-7-114190 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 5/05 101 C08G 64 / 14

Claims (15)

(57) [Claims] 1. An electrode comprising a photosensitive layer provided on a conductive support.
In the photoreceptor, the photosensitive layer contains a polycarbonate resin represented by the following general formula (I).
Electrophotographic photoreceptor . -General formula (I) (In the above formula, at least one of the terminal groups of X ₁ and X ₂ represents a group selected from a group having a hindered phenol structure and a group having a hindered amine structure, and R represents a group necessary for constituting polycarbonate. Represents the viscosity average molecular weight of the entire polycarbonate resin is 3000
Represents an integer that can be in the range of ~ 300,000. ) 2. The compound according to claim 1, wherein at least one of X ₁ and X _{2 in} the general formula (I) has a hindered phenol structure represented by the following general formula (II). Electrophotographic photoreceptor . -General formula (II) (In the above formula, R ₁ and R ₈ represent a branched alkyl group;
_{2 to} R ₇ each independently represent hydrogen, an alkyl group, an aryl group or an alkoxy group, n represents an integer of 1 to 3, and Y ₁ is selected from a linking group represented by the following structural formula . Embedded image (In the above formula, R _{9 to} R ₁₃ are each independently hydrogen,
A represents a kill group, an aryl group, or an alkoxy group;
Represents an integer of 0. )) 3. The compound according to claim 1, wherein at least one of the terminal groups of X ₁ and X _{2 in} the general formula (I) has a hindered phenol structure represented by the following general formula (III). Electrophotographic photoreceptor . -General formula (III) (In the above formula, at least one of R ₁₄ and R ₁₅ is a branched alkyl group, the rest is an alkyl group, an aryl group or an alkoxy group, at least one of R ₁₆ and R ₁₇ is a branched alkyl group, and the rest is a branched alkyl group. Represents an alkyl group, an aryl group or an alkoxy group, and b and c each independently represent 1 to
3 represents an integer, m represents an integer of 1 to 3, and A represents -O-
Or -NH-, and Y ₂ represents a linking group or a single bond. ) 4. The electron according to claim 1, wherein at least one of the terminal groups of X ₁ and X _{2 in} the general formula (I) has a hindered amine structure represented by the following general formula (IV). Photoreceptor . -General formula (IV) ( Wherein at least one of Q _{1 to} Q ₃ is a group represented by the following structural formula; The remainder is an alkyl group or the following structural formula: And Q ₄ represents hydrogen or a group having 1 to 13 carbon atoms.
Represents an alkyl group. ) 5. The electron according to claim 1, wherein at least one of the terminal groups of X ₁ and X _{2 in} the general formula (I) has a hindered amine structure represented by the following general formula (V). Photoreceptor . -General formula (V) (In the above formula, n represents an integer with which the viscosity average molecular weight of the entire polycarbonate resin can be in the range of 3000 to 300,000. ) 6. R in the general formula (I) is the following general formula (VI)
The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is represented by a structural unit represented by: -General formula (VI) (In the above formula, R _{18 to} R ₂₁ each independently represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 5 carbon atoms,
They are an aryl group having 6 to 12 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, and these groups may be substituted. Z represents a group represented by the following structural formula. Embedded image (In the above formula, R _{22 to} R ₂₉ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or R ₂₂ and R ₂₃ , R
₂₆ and R ₂₈ or R ₂₇ and R ₂₉ are bonded together to represent a group forming a carbocyclic or heterocyclic ring, and these groups may be substituted. d represents 0 or 1. )) 7. The compound according to claim 1, wherein R in the general formula (I) is represented by a structural unit represented by the following structural formula.
The electrophotographic photosensitive member according to any one of the above. Embedded image 8. A photosensitive layer, the electrophotographic photosensitive according to any one of claims 1-7, characterized in that a single layer structure containing both a charge generating material and a charge-transporting material in the same layer body. 9. The photosensitive layer is functionally separated into a charge transport layer containing at least a charge transport material and a charge generation layer containing a charge generation material .
8. The electrophotographic photoreceptor according to any one of 7 . 10. The charge transporting material of the following general formula (VI
The electrophotographic photoreceptor according to claim 8 or 9 , wherein the photosensitive layer contains a benzidine compound represented by the formula (I). -General formula (VII) (In the above formula, R ₃₀ and R ₃₀ ′ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and R ₃₁ , R ₃₁ ′, R ₃₂ and R ₃₂ ′ are the same. And e may represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group, and e, e ', f, and f' each independently represent an integer of 1 or 2. ) 11. The charge transporting material of the following general formula (VI
The electrophotographic photoreceptor according to claim 8 , wherein the photosensitive layer contains the triarylamine compound represented by the formula (II). -General formula (VIII) (In the above formula, R ₃₃ and R ₃₄ may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and g and h each represent an integer of 1 or 2. R ₃₅ Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ) 12. A Bragg angle (2θ ± 0.2) of an X-ray diffraction spectrum using Cuka radiation as a charge generation material.
°), at least 7.4 °, 16.6 °, 2
The electrophotographic photoconductor according to any one of claims 8 to 11 , wherein the photosensitive layer contains dichlorogallium phthalocyanine having diffraction peaks at 5.5 ° and 28.3 °. 13. A Bragg angle (2θ ± 0.2) of an X-ray diffraction spectrum using Cuka radiation as a charge generation material.
°) at least 7.5 °, 9.9 °, 12.
5 °, 16.3 °, 18.6 °, 25.1 °, 28.1
The photosensitive layer contains hydroxygallium phthalocyanine having a diffraction peak at a position of °.
The electrophotographic photosensitive member according to any one of 8 to 11 , wherein 14. A Bragg angle (2θ ± 0.2) of an X-ray diffraction spectrum using Cukα ray as a charge generation material.
°), at least 9.5 °, 11.7 °, 1
The electrophotographic photoreceptor according to any one of claims 8 to 11 , wherein the photosensitive layer contains titanyl phthalocyanine having diffraction peaks at 5.0 °, 24.1 °, and 27.3 °. . 15. An electrophotographic apparatus charging devices is a contact charging device, an electrophotographic apparatus characterized by using the electrophotographic photoreceptor according to any one of claims 1 to 14.