JPH1020513A - Organic electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an org. electrophotographic photoreceptor less liable to wear, hardly causing the deterioration of toner filming resistance and maintaining superior electrophotographic characteristics even when the photoreceptor is repeatedly used over a long time. SOLUTION: This org. electrophotographic photoreceptor is obtd. by disposing a photosensitive layer on an electrically conductive substrate and has a surface formed with a material whose surface has 0.01-0.15μm center line average roughness Ra. When this surface is subjected to an abrasion test by which abrasive paper contg. Al2 O3 grains of 3μm as abrasive grains is moved back and forth 2,000 times under 500g load, the center line average roughness Ra is increased to <=17μm after the test.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly, to electrophotographic photoreceptors which are less likely to deteriorate in electrophotographic characteristics and toner filming resistance even when used repeatedly for a long period of time. The present invention relates to an organic electrophotographic photoreceptor (OPC) that can be suitably used.

[0002]

2. Description of the Related Art In the recent field of electrophotography, a laminated organic electrophotographic photoreceptor, that is, a photosensitive layer has a charge generation layer (CGL) for generating charges upon exposure and a charge transport layer (CTL) for transporting charges. ) And a single-layer type organic electrophotographic photoreceptor having a single layer in which a charge generating substance and a charge transporting substance are dispersed in a binder resin is proposed. Has been used.

On the other hand, an organic electrophotographic photosensitive member is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to an applied electrophotographic process. In particular, for a photoreceptor that is used repeatedly, a surface layer of the photoreceptor, that is, a layer located farthest from a substrate (usually a conductive substrate),
During corona charging, toner development, transfer to paper, cleaning processing, and the like, electrical and mechanical external forces are directly applied, so that durability against them is required. In particular,
Durability against abrasion and scratches on the surface due to friction, deterioration of the surface due to ozone generated at the time of corona charging at high temperatures, and the like is required. Therefore, in order to respond to such a demand, the charge transport layer of the above-mentioned stacked type organic electrophotographic photoreceptor and the binder resin of the photosensitive layer of the single layer type organic electrophotographic photoreceptor are compatible with the charge transport material. Polycarbonate resins made from bisphenol A or bisphenol Z, which has good mechanical strength and high mechanical strength, have been widely used. However, the use of this polycarbonate resin made of bisphenol A or bisphenol Z is not sufficient to satisfy the above requirements.

That is, when a polycarbonate resin made of bisphenol A or bisphenol Z is dissolved in a solvent to prepare a coating solution for forming a photosensitive layer, the coating solution is whitened or gelled, and In some cases, the photosensitive layer after drying may be crystallized. In the portion where the crystallization has occurred, there is no light decay, and the charge remains as a residual potential,
Appears as a defect in image quality.

[0005] In addition, a photoreceptor using a polycarbonate resin made of bisphenol A or bisphenol Z is inferior in durability due to insufficient abrasion of the surface due to insufficient surface hardness.

In order to solve these problems, introduction of a biphenol skeleton as a rigid component (Japanese Patent Application Laid-Open No. 4-179951) and introduction of a specific cross-linked structure (Japanese Patent Application Laid-Open No. 4-291)
348) and the like have been proposed. By the use of these resins, the abrasion loss and film abrasion loss of the electrophotographic photosensitive member were improved to some extent. However, even with these resins, there is a problem in abrasion resistance, and even when the characteristics in the initial stage of use are good, the organic electrophotographic photoreceptor is worn by repeating printing and the like, and as a result, the electrophotographic characteristics deteriorate, A phenomenon such as so-called toner filming that toner adheres to the surface of the photoconductor occurs. Heretofore, phenomena such as deterioration of electrophotographic characteristics have been considered to be caused by simple increases in the amount of wear and the amount of film scraping. However, there have been many cases in which the degree of deterioration such as electrophotographic characteristics and toner filming is completely different even though the wear amount is almost the same.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and is based on the use of a polycarbonate made of bisphenol A, bisphenol Z or biphenol as a binder resin, and a crosslinked polycarbonate having a specific structure. Solving the above-mentioned problems observed in the electrophotographic photoreceptor, has good compatibility with the charge transport material, and does not cause whitening or gelation even when dissolved in a solvent, and has high surface hardness and abrasion resistance An object of the present invention is to provide an organic electrophotographic photoreceptor which is produced using a polycarbonate having the following characteristics and maintains excellent electrophotographic properties and toner filming resistance over a long period of time.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors analyzed in detail the abrasion phenomenon of the organic electrophotographic photosensitive member, and found the cause of deterioration of the electrophotographic characteristics and toner filming resistance. The research was repeated to find out a factor that becomes a factor and to find a method of quantifying the factor. As a result, it has been found that not only the amount of wear but also the surface roughness after the wear is a major factor in the deterioration of the electrophotographic characteristics and the toner filming resistance of the organic electrophotographic photosensitive member. As a method for quantifying the surface roughness due to abrasion that affects the deterioration of electrophotographic characteristics and toner filming resistance, a specific abrasion test is performed, and the center line average roughness Ra value is determined in accordance with JIS B0601. Was also found to be effective.
The present inventors have completed the present invention based on these findings.

That is, according to the present invention, there is provided an organic electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate.
When a polishing test was performed in which abrading particles of Al ₂ O ₃ 3 μm were reciprocated 2,000 times on a surface having an a value of 0.01 to 0.15 μm with a load of 500 g, the center line average roughness after the polishing test was determined. An object of the present invention is to provide an organic electrophotographic photosensitive member having a surface formed of a substance having a Ra value of 0.17 μm or less.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the center line average roughness Ra was measured in accordance with JIS B0601.

The structure of the organic electrophotographic photoreceptor of the present invention is not particularly limited as long as it has a photosensitive layer on a conductive substrate and a surface layer formed of the above-mentioned specific substance. Any known organic electrophotographic photoreceptor of various types such as a layer type and a lamination type may be used.

The laminated organic electrophotographic photoreceptor generally has a photosensitive layer comprising at least one charge generating layer containing a charge generating substance and at least one charge transporting layer containing a charge transporting substance and a binder resin. The single-layer organic electrophotographic photoreceptor generally has a photosensitive layer having a charge generating substance,
It is composed of only one layer containing a charge transport material and a binder resin. In addition, these photosensitive layers may have a surface protective layer on the surface.

In the present invention, in order to form the surface of the photosensitive layer with a substance having a center line average roughness Ra value of 0.17 μm or less after the above-mentioned specific deterioration test, a single-layer type organic electrophotographic photosensitive material is required. In the case of a body, as a binder resin in a photosensitive layer, in the case of a laminated organic electrophotographic photosensitive member, as a binder resin in a charge transport layer or a charge generation layer to be a surface layer,
Further, in a laminate type or single-layer type organic electrophotographic photoreceptor having a surface protective layer, it is preferable to use a layer containing crosslinked polycarbonate as the surface protective layer. Crosslinked polycarbonate may be used for both the binder resin and the surface protective layer in the photosensitive layer.

An organic electrophotographic photoreceptor using a crosslinked polycarbonate as a binder resin usually has a photosensitive layer containing a crosslinkable polycarbonate before crosslinking and optionally a crosslinking agent and a radical initiator formed on a conductive substrate. Thereafter, the crosslinkable polycarbonate is produced by crosslinking. Organic electrophotographic photoreceptors having a surface protective layer usually form a photosensitive layer on a conductive substrate and then form a layer comprising the crosslinkable polycarbonate and, if necessary, a crosslinking agent or a radical initiator on the photosensitive layer. And then crosslinking the crosslinkable polycarbonate.

[0015] Crosslinking of the crosslinkable polycarbonate can be carried out by a crosslinking reaction by an ionic mechanism using a crosslinking agent and by a radical mechanism.

The crosslinking reaction by an ionic mechanism includes crosslinking by reaction between a crosslinkable polycarbonate having a nucleophilic group and an electrophilic crosslinking agent, crosslinking by reaction between a crosslinkable polycarbonate having an electrophilic group and a nucleophilic crosslinking agent, Crosslinkable polycarbonate having a reactive group that causes polymerization by a Lewis acid and crosslinking by a Lewis acidic crosslinking agent, and crosslinking by a reaction between a crosslinkable polycarbonate having a nucleophilic group and a crosslinkable polycarbonate having an electrophilic group. .

Examples of the nucleophilic group include -OH (including -OH generated by ring opening of an epoxy group), -SH, -COOH,
—NH ₂ , —NRH, and —NR ₂ . Examples of the electrophilic group include an epoxy group, a halogen group, a carbonyl group, a cyano group, an isocyanate group, an imino group, and a sulfonate group. Examples of the reactive group that causes a polymerization reaction by the Lewis acid include an epoxy group, a carbonyl group, and a vinyl group.

Examples of the nucleophilic crosslinking agent include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, N-aminoethylpiperazine, bis-aminopropylpiperazine, dicyandiamide, and polyoxypropylenediamine. Aromatic amines such as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, and isophoronediamine; for example, 4,4'-diaminodiphenylmethane;
Tertiary amines such as 4,4'-diaminodiphenyl ether, diaminodiphenylsulfone, phenylenediamine, toluylenediamine, xylylenediamine, and the like, for example, dimethylaminomethylphenol, furthermore, ketimine, imidazole, melamine resin, urea resin, phenol resin and the like. No.

Examples of the electrophilic crosslinking agent include acid anhydrides such as maleic anhydride, dodecenylsuccinic anhydride, chlorendic anhydride, sebacic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Cyclopentane / tetracarboxylic dihydrate, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyl / tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl endo Methylenetetrahydrophthalic anhydride, methylnadic anhydride, etc., isocyanates, block isocyanates, epoxy resins, for example,
Bisphenol A type epoxy resin (epoxy equivalent: usually 150 to 4000), novolak type epoxy resin (epoxy equivalent: usually 150 to 4000), glycidyl ester of polybasic acid, glycidyl ether of polyhydric alcohol, glycidyl of polyvalent amine Glycidyl-type resins such as adducts), and non-glycidyl-type resins such as dicyclopentadiene dioxide and vinylcyclohexene dioxide.

As the Lewis acidic crosslinking agent, a boron halide complex compound, for example, a boron trifluoride / monomethylamine complex compound, a boron trifluoride / triethanolamine complex compound, a boron trifluoride / piperidine complex compound, or a trifluoride compound And a boron trifluoride / amine complex compound.

Of the above, all combinations of a nucleophilic group and an electrophilic cross-linking agent, all combinations of an electrophilic group and a nucleophilic cross-linking agent, and a reactive group which causes a polymerization reaction with a Lewis acid and a Lewis acid The ion-crosslinked polycarbonate can be produced by all combinations of the crosslinking agents. Among them, preferred combinations are as follows. (1) When the crosslinkable polycarbonate is -NH as a nucleophilic group
Those having ₂ or -NHR _2, the electrophilic crosslinker is an epoxy resin; (2) -CO-crosslinking polycarbonate as nucleophilic group
₂ H or - (CO) those having ₂ O, the electrophilic crosslinker is an epoxy resin; (3) -OH crosslinking polycarbonate as nucleophilic group
Wherein the electrophilic crosslinking agent is an epoxy resin; and (4) the crosslinking polycarbonate is -SH as a nucleophilic group.
(5) the crosslinkable polycarbonate has an epoxy group as the electrophilic group, and the nucleophilic crosslinker is an aliphatic polyamine; (6) crosslinkability The polycarbonate has an epoxy group as a reactive group that causes a polymerization reaction by a Lewis acid, and the Lewis acidic crosslinking agent is boron halide.

In order to obtain the substance having the above-mentioned specific anti-wear property of the present invention, the present inventors have specifically proposed (1) to (4)
The crosslinkable polycarbonate (6) is composed of a repeating unit (I) represented by the following general formula (I) and a repeating unit (IV) represented by the following general formula (IV). 2 of a solution having a concentration of 0.5 g / dl
It has been found that it is preferable to use a crosslinkable polycarbonate having a reduced viscosity at 0 ° C of 0.1 to 20.0 dl / g.

[0023]

Embedded image [Wherein, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 11 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. , Y is a single bond or -O-, -CO-, -S-,-
SO—, —SO ₂ —, —CR ³ R ⁴ — (R ³ and R ⁴ are each independently a hydrogen atom, a trifluoromethyl group,
And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ), 1,1- having 5 to 11 carbon atoms
A cycloalkylidene group, an α, ω-alkylene group having 2 to 12 carbon atoms or the following formula (a)

[0024]

Embedded image (Wherein, c is an integer of 0 to 4), a and b each independently represent an integer of 0 to 4;
Is

[0025]

Embedded image And FG is

[0026]

Embedded image (In the formula, h represents an integer of 0 to 4, and R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Represents.)
Wherein R ⁵ and R ⁶ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or Represents 6 to 12 substituted or unsubstituted aryloxy groups, d, e, f and g each independently represent an integer of 0 to 4, provided that d + e = 1 to 8, d + f = 0 to 4, e
+ G = 0 to 4, and R ⁹ and R ¹⁰ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a substituted or unsubstituted 6 to 12 carbon atoms. Represents an aryl group or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, i, j, k and l each independently represent an integer of 0 to 3, provided that i + j = 1 to 6, i + k
= 0 to 3, and j + 1 = 1 to 3. The crosslinkable polycarbonate may be either linear or cyclic, and further has a special terminal structure or a special branched structure at the polymer terminal by using a terminal terminator or a branching agent during the synthesis. May be introduced.

The reduced viscosity at 20 ° C. of a 0.5 g / dl solution of this crosslinkable polycarbonate in methylene chloride as a solvent has a reduced viscosity of 0.1 to 20.0 dl / g, preferably 0.2 to 2 dl / g. Preferably 0.5 to 2 dl /
g. When a crosslinkable polycarbonate having a reduced viscosity of less than 0.1 dl / g is used, the surface hardness of a layer containing the obtained crosslinked polycarbonate as a binder resin becomes insufficient even after crosslinking, and the surface of the organic electrophotographic photosensitive member is worn. And the Ra value after the deterioration test is 0.17.
In some cases, it may not be possible to form a layer made of a substance having a thickness of less than μm. On the other hand, when a crosslinkable polycarbonate having a reduced viscosity of more than 20.0 dl / g is used, the solution viscosity of the crosslinkable polycarbonate increases, and it may be difficult to produce an organic electrophotographic photosensitive member by applying a coating liquid.

In the crosslinkable polycarbonate comprising the repeating units represented by the above general formulas (I) and (IV), the ratio of the repeating unit (IV) to the total moles of the repeating units (I) and (IV) is as follows. Usually, 1 to 90 mol%, preferably 1 to 30 mol%, more preferably 10 to
It is desirably in the range of 30 mol%. When the proportion of the repeating unit (IV) is less than 1 mol%, the durability of the layer containing the crosslinked product of the crosslinkable polycarbonate is insufficiently improved, or the Ra value after the deterioration test is 0.17.
In some cases, it is not possible to form a layer made of a substance having a thickness of not more than μm, and if it exceeds 90 mol%, the layer containing the crosslinked polycarbonate is also brittle, and the durability may be poor.

Of the above crosslinkable polycarbonates, those comprising a repeating unit (I) and a repeating unit (IV) in which W is represented by the general formula (V), that is, those represented by the general formula (I) A crosslinkable polycarbonate comprising a repeating unit (I) represented by the following general formula (II) and a repeating unit (II) represented by the following general formula (II):

[0030]

Embedded image (Wherein, R ¹ , R ² , a, b, Y, FG, R ⁵ , R ⁶ , d,
e, f and g have the same meaning as above. ) And a repeating unit (I) and a repeating unit (V) wherein W is represented by the general formula (VI), that is, a repeating unit (I) represented by the general formula (I) and Crosslinkable polycarbonate comprising repeating unit (III) represented by general formula (III)

[0031]

Embedded image [Wherein, R ¹ , R ² , a, b, Y, FG, R ⁹ , R ¹⁰ ,
i, j, k and l have the same meaning as above. ) Are preferably used.

R ¹ , R ² , R ⁵ , R ⁶ , R ^{9 in the} above general formula
And the halogen atom represented by R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is particularly preferred.

In the above formula, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have 1 to 6 carbon atoms
Examples of the alkyl group include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, isobutyl group, n
-Pentyl group, neopentyl group, n-hexyl group, and methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl are particularly preferable.

The carbon number represented by R ¹ and R ² in the above general formula is 5
Examples of the cycloalkyl group of Nos. 1 to 11 include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

The alkyloxy group having 1 to 4 carbon atoms represented by R ⁵ , R ⁶ , R ⁹ and R ¹⁰ in the above general formula includes methoxy, ethoxy, n-propyloxy, isopropoxy, n -Butoxy group, sec-butoxy group, ter
Examples include t-butoxy and isobutoxy, especially methoxy, ethoxy, ilopropoxy and tert.
-Butoxy groups are preferred.

In the above general formula, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have ⁶ to 1 carbon atoms.
Examples of the aryl group 2 include a phenyl group, a naphthyl group and a biphenylyl group, and a phenyl group is particularly preferable.

The aryloxy group having 6 to 12 carbon atoms represented by R ⁵ , R ⁶ , R ⁹ and R ¹⁰ in the above general formula includes, for example, phenoxy, naphthoxy and biphenyloxy, especially phenoxy Is preferred.

Examples of the substituent of the aryl group and the aryloxy group having 6 to 12 carbon atoms include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, and a substituent having 6 to 12 carbon atoms. Examples thereof include an aryl group and an aryloxy group having 6 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, and an aryl group having 6 to 12 carbon atoms.

The substituents R ¹ to R ¹⁰ may be different from each other, or two or more of them may be the same.

The crosslinkable polycarbonate before crosslinking of the crosslinked polycarbonate suitably used as the binder resin in the present invention can be synthesized, for example, by reacting a dihydric phenol with a carbonate-forming compound. As a synthesis method, for example, using phosgene or the like as a carbonate-forming compound, polycondensation with the dihydric phenols in the presence of a suitable acid binder, or using a bisaryl carbonate as a carbonate-forming compound, A method in which a transesterification reaction is performed can be given. There are no particular restrictions on the dihydric phenols,
One or more compounds can be arbitrarily selected from compounds including known compounds.

For example, the above-mentioned general formulas (I) and (IV)
The crosslinkable polycarbonate preferably comprising a repeating unit represented by the following general formula (VII):

[0042]

Embedded image (Wherein, R ¹ , R ² , a, b and Y have the same meanings as described above), and a divalent phenol represented by the following general formula (VIII) Phenol (VIII) and / or dihydric phenol (IX) represented by the following general formula (IX)

[0043]

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , FG, d, e, f,
g, i, j, k and l have the same meaning as described above. )
It is manufactured using

Specific examples of the dihydric phenols (VII) represented by the general formula (VII) include, for example, 4,4'-
Dihydroxybiphenyl, 3,3'-difluoro-4,
4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl 4,4'-dihydroxybiphenyls; bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) propane (alias: bisphenol A), 2,2-
Bis (3-methyl-4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) octane, 4,4
-Bis (4-hydroxyphenyl) heptane, 1,1-
Bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1
-Phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2
-(3-methyl-4-hydroxyphenyl) -2- (4
-Hydroxyphenyl) -1-phenylethane, bis (3-methyl-4-hydroxyphenyl) methane, 1,
1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 1,1-bis (2-butyl-4)
-Hydroxy-5-methylphenyl) butane, 1,1-
Bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-tert-
Butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2
-Tert-butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane,
1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1
-Bis (4-hydroxy-2-methyl-5-tert-
Pentylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-
4-hydroxyphenyl) methane, 2,2-bis (3-
Chloro-4-hydroxyphenyl) propane, 2,2-
Bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4
-Hydroxyphenyl) propane (alias: tetrafluorobisphenol A), 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane (alias: tetrachlorobisphenol A), 2,2-bis (3,5 -Dibromo-4-hydroxyphenyl) propane (alias: tetrabromobisphenol A), 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3,5-dichloro- 4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-
4-hydroxyphenyl) butane, 1-phenyl-1,
1-bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-hydroxyphenyl) -1,1,1,1 3,3,3-hexafluoropropane, 2,2-bis (3-phenyl-4-
Bis (4-hydroxyphenyl) alkanes such as hydroxyphenyl) propane and 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane; bis (4
Bis (4-hydroxyphenyl) ethers such as -hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) Bis (4-hydroxyphenyl) sulfides such as sulfides; bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone and the like (4-hydroxyphenyl) sulfones; 4,4'-dihydroxybenzophenone; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9- ( 4-hydroxyphenyl) -9
Examples include 9,9-bis (4-hydroxyphenylfluorenes) such as-(4-hydroxy-3-methylphenyl) fluorene.

Among these, preferred dihydric phenols are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl). )-
1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4'-dihydroxybiphenyl and bis (4-hydroxyphenyl) sulfone, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferred. Used for

These dihydric phenols may be used alone or in combination of two or more.

Examples of the dihydric phenol represented by the general formula (IV) include 3,3'-diglycidyl-4,
4'-dihydroxy-5,5'-diphenylbiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diglycidyl-4,4'-dihydroxybiphenyl, 3,3'-diglycidyl- 4,4'-
Dihydroxy-5,5'-dimethylbiphenyl, 3,
3'-diglycidyl-4,4'-dihydroxy-5,
5'-dimethoxybiphenyl, 3,3'-diglycidyl-4,4'-dihydroxy-5,5'-dichlorobiphenyl, 3,3'-diepoxy-4,4'-dihydroxybiphenyl, 3,3'-divinyl- 4,4'-dihydroxybiphenyl, 3,3'-diallyl-4,4'-dihydroxybiphenyl, 3,6-diglycidyl-2,7-
Dihydroxynaphthalene, 3,6-diallyl-2,7-
Dihydroxynaphthalene, 3,6-divinyl-2,7-
Dihydroxynaphthalene, 1,8-diallyl-2,7-
Dihydroxynaphthalene, 1,8-diglycidyl-2,
7-dihydroxynaphthalene, 3,8-diallyl-2,
7-dihydroxynaphthalene, 3,8-diglycidyl-
2,7-dihydroxynaphthalene and the like can be mentioned.

The epoxy group in the FG group, -NR
⁷ R ⁸ , —SH, —OH, and —CO ₂ H can also be introduced by a polymer reaction after polycarbonate synthesis.
For example, among the above crosslinkable polycarbonates, FG is

[0049]

Embedded image (Wherein h has the same meaning as described above), the following general formula (X )) And / or the repeating unit (XI) represented by the following general formula (XI)

[0050]

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , d, e, f, g, h,
i, j, k and l have the same meaning as above. ) May be produced as a precursor by an oxidation reaction using metachloroperbenzoic acid. For example, specifically, it can be obtained by reacting an excess amount of metachloroperbenzoic acid with methylene chloride in methylene chloride at room temperature, for example, for about 24 hours.

Examples of the dihydric phenol having a carbon-carbon double bond to be the repeating units (X) and (XI) of the general formulas (X) and (XI) include, for example, 3,3'-diallyl-4 4,4'-dihydroxy-5,5'-diphenylbiphenyl, 3,3'-divinyl-4,4'-dihydroxybiphenyl, 3,3'-diallyl-4,4'-dihydroxybiphenyl, 3,3'-divinyl -4, 4 '
-Dihydroxy-5,5'-dimethoxybiphenyl,
3,6-diallyl-2,7-dihydroxynaphthalene,
3,6-divinyl-2,7-dihydroxynaphthalene,
1,8-diallyl-2,7-dihydroxynaphthalene,
3,8-diallyl-2,7-dihydroxynaphthalene and the like.

These dihydric phenols may be used alone or in combination of two or more.

Further, in addition to the above-mentioned dihydric phenols as a raw material, a branching agent and a terminal terminator may be used as necessary.

As a branching agent, a phenol or carboxylic acid having a valency of 3 or more can be used.

Examples of branching agents include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,4-
Dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 1,3,3
5-tris (2-hydroxyphenyl) benzene, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl) propane, 2,4- Screw @ 2-
(4-hydroxyphenyl) -2-propyl} phenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4- Dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane,
Tetrakis (4- (4-hydroxyphenylisopropyl) phenoxy) methane, 1,4-bis (4 ′, 4 ″-
Dihydroxytriphenylmethyl) benzene, 2,4-
Dihydroxybenzoic acid, trimesic acid, cyanuric acid,
3,3-bis (3-methyl-4-hydroxyphenyl)
-2-oxo-2,3-dihydroindole, 3,3-
Bis (4-hydroxyaryl) oxindole, 5
-Chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like.

Among these, phloroglysin, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane and the like are preferably used.

As the terminal terminator, a monovalent carboxylic acid and its derivative, and a monovalent phenol can be used.

Specific examples include phenol, α-naphthol, β-naphthol, o-cresol, m-cresol, p-cresol, 2,3-xylenol,
4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-propylphenol, p-butylphenol, p-pentylphenol,
p-hexylphenol, p-heptylphenol, p
-Octylphenol, p-nonylphenol, p-decylphenol, p-undecylphenol, p-dodecylphenol, p-isopropylphenol, pt
tert-butylphenol, 2,6-dimethyl-pt
tert-butylphenol, 2-tert-pentyl-
4-methylphenol, 3-methyl-6-tert-butylphenol, 2-methyl-4,6-di-tert-
Butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-tert-pentylphenol, 2,
4,6-tri-tert-butylphenol, p-phenylphenol, 2,6-di-tert-butyl-4-
Phenylphenol, 2,6-di-sec-butyl-4
-Methylphenol, o-anisole, m-anisole, p-anisole, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, p-ethoxyphenol , O-aminophenol,
m-aminophenol, p-aminophenol, p-cyanophenol, p-nitrophenol, 3-methyl-
6-isopropylphenol, 2-methyl-5-isopropylphenol, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, Perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluoropentadecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, 2H, 2H-perfluoropentanoic acid, 2H, 2H- Perfluorohexanoic acid, 2H, 2H
-Perfluoroheptanoic acid, 2H, 2H-perfluorooctanoic acid, 2H, 2H-perfluorononanoic acid, 2
H, 2H-perfluorodecanoic acid, 2H, 2H-perfluoroundecanoic acid, 2H, 2H-perfluorododecanoic acid, 2H, 2H-perfluorotridecanoic acid, 2H,
2H, 3H, 3H-perfluorohexanoic acid, 2H, 2
H, 3H, 3H-perfluoroheptanoic acid, 2H, 2
H, 3H, 3H-perfluorooctanoic acid, 2H, 2
H, 3H, 3H-perfluorononanoic acid, 2H, 2H,
3H, 3H-perfluorodecanoic acid, 2H, 2H, 5H
-Perfluoropentanoic acid, 2H, 2H, 6H-perfluorohexanoic acid, 2H, 2H, 7H-perfluoroheptanoic acid, 2H, 2H, 8H-perfluorooctanoic acid,
2H, 2H, 9H-perfluorononanoic acid, 2H, 2
H, 10H-perfluorodecanoic acid, 2H, 2H, 11
H-perfluoroundecanoic acid, 2H, 2H, 12H-
Perfluorododecanoic acid, 2H, 2H, 13H-perfluoroundecanoic acid, or an acid halide thereof, p
-(Perfluoropentyl) phenol, p- (perfluorohexyl) phenol, p- (perfluoroheptyl) phenol, p- (perfluorooctyl) phenol, p- (perfluorononyl) phenol, p-
(Perfluorodecyl) phenol, p- (perfluoroundecyl) phenol, p- (perfluorododecyl) phenol, p- (perfluorotridecyl) phenol, p- (perfluorotetradecyl) phenol, p- (per Fluoropentadecyl) phenol, p
-(Perfluorobutyloxy) phenol, p- (perfluoropentyloxy) phenol, p- (perfluorohexyloxy) phenol, p- (perfluoroheptyloxy) phenol, p- (perfluorooctyloxy) phenol, p -(Perfluorononyloxy) phenol, p- (perfluorodecyloxy) phenol, p- (perfluoroundecyloxy) phenol, p- (perfluorododecyloxy)
Phenol, p- (perfluorotridecyloxy) phenol, p- (perfluorotetradecyloxy) phenol, p- (perfluoropentadecyloxy) phenol, 4-perfluorooctyl-2,3,5,6
-Tetrafluorophenol, 4-perfluorononyl-2,3,5,6-tetrafluorophenol, 4-perfluorodecyl-2,3,5,6-tetrafluorophenol, 4-perfluoroundecyl-2, 3,5
6-tetrafluorophenol, 4-perfluorododecyl-2,3,5,6-tetrafluorophenol, 4
-Perfluorotridecyl-2,3,5,6-tetrafluorophenol, 4-perfluorotetradecyl-
2,3,5,6-tetrafluorophenol, 4-perfluoropentadecyl-2,3,5,6-tetrafluorophenol, p-tert-perfluorobutylphenol, 3-methyl-4-perfluorononylphenol, p -(2- (1H, 1H-perfluorooctyloxy) -1,1,1,3,3,3-hexafluoro-2
-Propyl) phenol, p- (2- (1H, 1H-perfluorononyloxy) -1,1,1,3,3,3-
Hexafluoro-2-propyl) phenol, p- (2
-(1H, 1H-perfluorodecyloxy) -1,
1,1,3,3,3-hexafluoro-2-propyl)
Phenol, p- (2- (1H, 1H-perfluoroundecyloxy) -1,1,1,3,3,3-hexafluoro-2-propyl) phenol, p- (2- (1
H, 1H-perfluorododecyloxy) -1,1,
1,3,3,3-hexafluoro-2-propyl) phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p- (1H, 1H-perfluoropentyloxy) phenol, p- (1H, 1H-perfluorohexyloxy) phenol, p- (1H,
1H-perfluoroheptyloxy) phenol, p-
(1H, 1H-perfluorooctyloxy) phenol, p- (1H, 1H-perfluorononyloxy) phenol, p- (1H, 1H-perfluorodecyloxy) phenol, p- (1H, 1H-perfluoroun) Decyloxy) phenol, p- (1H, 1H-perfluorododecyloxy) phenol, p- (1H, 1H
-Perfluorotridecyloxy) phenol, perfluoropentyl p-hydroxybenzoate, perfluorohexyl p-hydroxybenzoate, perfluoroheptyl p-hydroxybenzoate, perfluorooctyl p-hydroxybenzoate, p-hydroxybenzoic acid Perfluorononyl, perfluorodecyl p-hydroxybenzoate, perfluoroundecyl p-hydroxybenzoate,
perfluorododecyl p-hydroxybenzoate, (p-
(Hydroxybenzyl) perfluorohexane, (p-hydroxybenzyl) perfluoroheptane, (p-hydroxybenzyl) perfluorooctane, (p-hydroxybenzyl) perfluorononane, (p-hydroxybenzyl) perfluorodecane, (p- (Hydroxybenzyl) perfluoroundecane, (p-hydroxybenzyl) perfluorododecane, and the like.

Of these, p-
(Tert-butyl) phenol, p-phenylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol,
p-tert-perfluorobutylphenol, 1-
(P-hydroxybenzyl) perfluorodecane, p-
(2- (1H, 1H-perfluorotridecyloxy)
-1,1,1,3,3,3-hexafluoropropyl)
Phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-perfluorononanoic acid Is mentioned.

The terminal terminating agent and the branching agent are used in the presence of the above-mentioned dihydric phenols.
A method in which the reaction is carried out from the beginning with the above two or three kinds of raw material compounds to carry out a reaction to increase the molecular weight. Method: After preparing an oligomer composed of dihydric phenols, first reacting the oligomer with a terminal terminator in the oligomer, and then coexisting a branching agent to increase the molecular weight. After preparing the compound, various methods can be employed, such as a method in which a branching agent is allowed to coexist with the oligomer to react with the oligomer, and then a terminal stopper is coexisted to increase the molecular weight.

The reaction of performing polycondensation in the presence of an acid binder using various carbonyl halides such as phosgene, haloformates such as chloroformate, etc. as the carbonate-forming compound, Usually, it is carried out in a solvent. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably employed.

The use ratio of the carbonate-forming compound is as follows:
What is necessary is just to adjust suitably considering the stoichiometric ratio (equivalent) of reaction.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate;
An organic base such as pyridine or a mixture thereof is used.

The proportion of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, the total number of moles of the dihydric phenols used (normally 1 mole is 2 moles)
Equivalent to 2 equivalents) or 2 equivalents or more,
It is preferable to use 2 to 10 equivalents of an acid binder.

As the solvent, various solvents such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. Representative examples include, for example, hydrocarbon solvents such as toluene and xylene,
Halogenated hydrocarbon solvents such as methylene chloride, chloroform, and chlorobenzene are exemplified. The interfacial polycondensation reaction may be performed using two types of solvents that do not mix with each other.

In order to promote the polycondensation reaction, it is desirable to carry out the reaction by adding a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added. The reaction is
Usually, it is carried out at a temperature in the range of 0 to 150C, preferably 5 to 40C. The reaction pressure can be any of reduced pressure, normal pressure and pressurized pressure, but usually, it can be suitably performed at normal pressure or about the self-pressure of the reaction system. The reaction time depends on the reaction temperature and the like, but is usually about 0.5 minute to 10 hours, preferably about 1 minute to 2 hours.

Also, a two-step method in which a part of the reaction material comprising dihydric phenols is reacted with a carbonate-forming substance to form an oligomer, and then the remaining reaction materials are added to complete the polycondensation. Can also be used.
According to such a two-step method, the control of the reaction is easy and the molecular weight can be controlled with high accuracy.

The bisaryl carbonate used in the latter transesterification method between a dihydric phenol and a bisaryl carbonate includes, for example, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p- Chlorophenyl carbonate, dinaphthyl carbonate and the like can be mentioned.

The reaction format of this transesterification method is as follows.
A melt polycondensation method, a solid phase polycondensation method and the like are preferred. When performing the melt polycondensation method, a dihydric phenol and a bisaryl carbonate are mixed and reacted in a molten state at a high temperature under reduced pressure. The reaction is usually performed at a temperature in the range of 150 to 350C, preferably 200 to 300C. In the case of performing the solid-phase polycondensation method, a dihydric phenol and a bisaryl carbonate are mixed, and the mixture is heated to a temperature equal to or lower than the melting point of the resulting crosslinkable polycarbonate in a solid state to perform polycondensation. In any case, at the final stage of the reaction, the degree of reduced pressure is preferably adjusted to 1 mmHg or less, and phenols derived from the bisaryl carbonate generated by the transesterification are distilled out of the system. The reaction time depends on the reaction temperature and the degree of pressure reduction, but is usually about 1 to 4 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, and the reaction may be carried out by adding the above-mentioned molecular weight regulator, antioxidant and the like, if desired.

The reduced viscosity of the obtained crosslinkable polycarbonate can be adjusted to the above-mentioned range by various methods such as selection of the reaction conditions and adjustment of the amounts of the branching agent and the terminal stopper. . Also, in some cases,
Appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction,
Crosslinking treatment, partial decomposition treatment, etc.) to obtain a crosslinkable polycarbonate having a predetermined reduced viscosity.

The amount of the crosslinking agent to be used is generally 0.01 to 1.0 part by weight, preferably 0.05 to 0.5 part by weight, based on 1 part by weight of the crosslinkable polycarbonate. If the amount of the crosslinking agent used is less than 0.01 part by weight, the crosslinking does not proceed sufficiently. May adversely affect photographic properties.

If necessary, a curing accelerator such as a phenolic, triphenyl phosphate, tertiary amine, imidazole or polymercaptan compound may be added.

The cross-linking reaction of the cross-linkable polycarbonate by the ionic mechanism can be performed by coating a photosensitive layer material containing the cross-linkable polycarbonate on a conductive substrate, or by photo-sensitizing the surface protective layer material containing the cross-linkable polycarbonate. After coating on the layer, known literature on crosslinking agents (Taiseisha, Crosslinking Agent Handbook, 244-257, 1981, etc.),
Known literature on polycarbonate (Nikkan Kogyo Co., Ltd., Plastics Material Account [5], polycarbonate resin, 39
, P. 43, etc.), and known methods relating to epoxy resins (adhesion technology, pages 14, 3, 1-33, 1994, etc.).

For example, the cross-linking reaction conditions differ depending on the combination of the cross-linkable polycarbonate, the cross-linking agent and the like, but the cross-linking temperature is 50 ° C. to 250 ° C., preferably 100 to 200 ° C.
It is preferable to select a combination in which the crosslinking temperature is within 50 hours, preferably 1 to 10 hours. If the crosslinking temperature is lower than 50 ° C., the storage stability of the resin solution is deteriorated, and if it exceeds 250 ° C., the charge generating substance, the charge transporting substance and the like are deteriorated by heating, which may adversely affect the electrophotographic characteristics. On the other hand, when the crosslinking time exceeds 50 hours, the deterioration of the charge generating substance, the charge transporting substance, and the like due to heating progresses, and the productivity of the organic electrophotographic photosensitive member deteriorates.

On the other hand, examples of the crosslinking reaction by a radical mechanism include a crosslinking reaction of a crosslinkable polycarbonate having a vinyl group.

Crosslinking of the crosslinkable polycarbonate having a vinyl group by a radical mechanism can be performed thermally or photochemically. The crosslinking reaction by heat can be easily achieved by adding a crosslinking agent as needed in the presence of a radical initiator and heating. As a radical initiator, the half-life at 50 to 100 ° C is 1 to
10 hours is preferable from the viewpoint of the process. Examples include azo compounds such as bisisobutylnitrile and azobisisovaleronitrile. Examples of the crosslinking agent include diallyl compounds such as diallyl phthalate, diallylamine hydrochloride, and diallyl ether; and polyfunctional acrylates such as trimethylolpropane triacrylate, ethylene dimethacrylate, and pentaerythritol tetraacrylate. The amount of the crosslinking agent used is usually 1 part by weight of the crosslinkable polycarbonate,
0.01 to 1.0 part by weight, preferably 0.05 to 0.5 part
It is preferable to use parts by weight.

In the case where the crosslinkable polycarbonate is thermally crosslinked, a photosensitive layer material containing the crosslinkable polycarbonate is coated on a conductive substrate and then heated at 50 to 150 ° C.
Preferably, heating is performed at 70 to 150 ° C. If it is lower than 50 ° C., the thermal crosslinking reaction may not proceed sufficiently. Also, 15
When the temperature exceeds 0 ° C., components other than polycarbonate in the conductive substrate and the photosensitive layer may be deteriorated. The heating time is usually in the range of 5 minutes to 10 hours, preferably 10 minutes to 5 hours.

When the cross-linking reaction is carried out by irradiation with ultraviolet rays, the coating is preferably carried out in the presence of a cross-linking agent in addition to the photo-radical initiator, followed by irradiation with ultraviolet rays. Examples of the crosslinking agent used herein include a polyallyl compound, a polyfunctional acrylate, a polymercaptan, and a polyfunctional azide compound.

Examples of the polyallyl compound include diallyl compounds such as diallyl phthalate, diallylamine hydrochloride, and diallyl ether. Examples of the polyfunctional acrylate include trimethylolpropane triacrylate, ethylene glycol dimethacrylate, and pentaerythritol tetraacrylate. No. Examples of the polymercaptan include pentaerythritol tetra (3-mercaptopropionate), 1,4-dimercaptohexane, and the like. As the polyfunctional azide compound, an aromatic azide having relatively good thermal stability is preferably used. For example, 4,4'-diazidobenzalacetone, 2,6-di (4'-azidobenzal) cyclohexanone, 6-di (4'-azidobenzal) -4-methylcyclohexanone, di [4- (4'-azidophenyl) butadienyl] ketone, 4,4'-diazidochalcone, 4,4'-diazidostilbene-2, 2'-disulfonic acid and the like. The amount of these crosslinking agents used is usually 0.01 part by weight based on 1 part by weight of the crosslinkable polycarbonate.
To 1.0 part by weight, preferably 0.05 to 0.5 part by weight. In the photocrosslinking reaction using a polyallyl compound, a polyfunctional acrylate and a polymercaptan among the above crosslinking agents, coexistence of a photoradical initiator is preferable.

Examples of the photoradical initiator include benzophenone compounds such as benzophenone and Michler's ketone; diketone compounds such as benzyl and phenylmethoxydiketone; benzoin compounds such as benzoin ethyl ether and benzyl dimethyl ketal; and 2,4-diethylthioxanthone And the like, and quinone-based compounds such as 2-methylanthraquinone and camphorquinone are preferably used. If necessary, a photo-crosslinking reaction accelerator other than the above initiators, for example, an N, N-diethylaminobenzene derivative may be used in combination.

As an irradiation source, a mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a methyl halide lamp and the like are preferably used. The power of the light source is in the range of 1 mW / cm ^{2 to} 1 kW / cm ² , and the irradiation time depends on the power of the light source and the photoreaction speed, and is usually 1 second to 1 hour, preferably 1 second to 10 minutes.

The organic electrophotographic photoreceptor of the present invention can be suitably manufactured by using a crosslinkable polycarbonate as a binder resin material in the photosensitive layer and performing the above-mentioned crosslinking reaction.

As the material of the conductive substrate used in the organic electrophotographic photoreceptor of the present invention, various materials such as known materials can be used, and specifically, aluminum, nickel, chromium, palladium, titanium, Gold, silver, copper, zinc, stainless steel, molybdenum, indium, platinum, brass, lead oxide, tin oxide, indium oxide, ITO or graphite plates, drums and sheets, and coating by vapor deposition, sputtering, coating, etc. Conductive treated glass, cloth, paper or plastic films, sheets and seamless belts, plastic films, sheets and seamless belts laminated with metal foil such as aluminum, film-like sheets and seamless belts of metal plates, and electrode oxidation Metal drum treated with metal oxidation Etc. can be used.

The charge generation layer of the multi-layer type organic electrophotographic photosensitive member contains at least a charge generation material, and the charge generation layer is formed on a substrate as a base by vacuum deposition, sputtering,
By forming a layer of a charge generating substance by a CVD method or the like,
Alternatively, it can be obtained by forming a layer in which a charge generation substance is bound using a binder resin on a layer serving as a base. As a method for forming the charge generation layer using a binder resin, various methods such as a known method can be used, and usually, for example, a coating liquid in which a charge generation substance is dispersed or dissolved in a suitable solvent together with a binder resin. Is applied onto a predetermined base layer and dried.

As the charge generating substance, various substances such as known substances can be used. Specifically, selenium alone such as amorphous selenium and trigonal selenium, tellurium alone,
Selenium - tellurium alloys, selenium - alloy selenium such as arsenic alloys, selenium reducing compounds such as As ₂ Se ₃ or selenium-containing compositions, zinc oxide, cadmium sulfide, antimony sulfide, zinc sulfide, alloys such as CdS-Se, the Various inorganic materials such as inorganic materials composed of Group 12 and Group 16 elements, oxide semiconductors such as titanium oxide, silicon materials such as amorphous silicon, and non-metals such as τ-type metal-free phthalocyanine and χ-type metal-free phthalocyanine Phthalocyanine pigment, α
Type copper phthalocyanine, β type copper phthalocyanine, γ type copper phthalocyanine, ε type copper phthalocyanine, X type copper phthalocyanine, A type titanyl phthalocyanine, B type titanyl phthalocyanine, C type titanyl phthalocyanine, D type titanyl phthalocyanine, E type titanyl phthalocyanine, F
-Type titanyl phthalocyanine, H-type titanyl phthalocyanine, G-type titanyl phthalocyanine, K-type titanyl phthalocyanine, L-type titanyl phthalocyanine, M-type titanyl phthalocyanine, N-type titanyl phthalocyanine, Y-type titanyl phthalocyanine, oxo-titanium phthalocyanine, black angle in X-ray diffraction diagram 2θ is 27.3 ±
Metal phthalocyanine pigments such as titanyl phthalocyanine showing a strong diffraction peak at 0.2 degrees, cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyrylium dyes, and thiapyrylium dyes , Polyvinyl carbazole, squarium pigment, anthantrone pigment, benzimidazole pigment, azo pigment, thioindigo pigment, bisbenzimidazole pigment, quinoline pigment,
Lake pigment, oxazine pigment, dioxazine pigment, triphenylmethane pigment, azulhenium dye, squarium dye, triarylmethane dye, xanthine dye,
And thiazine dyes.

For example, a compound represented by the following general formula is preferably used.

[0087]

Embedded image [In the formula, Z ¹ , Z ² , Z ³ and Z ⁴ each independently form an aromatic hydrocarbon ring or a heterocyclic ring which may have a substituent together with the two carbon atoms on the pyrrole ring. M represents two hydrogen atoms or a metal atom or a metal compound which may have a ligand. ]

[0088]

Embedded image [In the formula, Ar ⁶ represents a t-valent residue having a conjugated system that may contain an aromatic hydrocarbon ring or a heterocyclic ring, and t represents 1
The above positive numbers, Cp represents a coupler residue having an aromatic hydroxyl group, and when t is 2 or more, each Cp may be the same or different. ]

[0089]

Embedded image [Wherein, X ² , X ³ , X ⁴ and X ⁵ each independently represent an oxygen atom, a sulfur atom, or a selenium atom, and R ^P and R ^Q represent an alkyl group or an aryl group having 1 to 12 carbon atoms. X ²
Alternatively, X ³ and R ^P and X ⁴ or X ⁵ and R ^Q may form a heterocyclic ring which may have a substituent. Examples of the fluorene-based disazo pigment include the following.

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image The following are examples of perylene pigments.

[0093]

Embedded image

[0094]

Embedded image Examples of the polycyclic quinone pigment include the following.

[0095]

Embedded image Examples of the anthantrone pigment include the following.

[0096]

Embedded image Examples of the dibenzpyrene quinone pigment include the following.

[0097]

Embedded image Examples of the pyranthrone pigment include the following.

[0098]

Embedded image These pigments can be used alone or in combination of two or more.

The charge generation layer has a thickness of 0.01 to 2.0 μm.
m is preferable, and 0.1 to 0.8 μm is more preferable.
If it is less than 0.01 μm, it is difficult to form the charge generation layer uniformly, and if it is more than 2.0 μm, the electrophotographic properties tend to deteriorate.

The binder resin used in the charge generation layer is not particularly limited, and various resins such as known ones can be used. Specifically, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, epoxy resin, phenol resin, polyamide, polyketone , Polyacrylamide, butyral resin, polyester, vinylidene chloride-vinyl chloride copolymer, methacrylic resin, polystyrene, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer , Silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal, Resulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, nitrocellulose, carboxy-methyl cellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyl toluene-styrene copolymer, soybean oil-modified alkyd resin, nitrated polystyrene, poly Methyl styrene, polyisoprene, polythiocarbonate, polyarylate, polyhaloallylate, polyallyl ether, polyvinyl acrylate,
A thermosetting resin such as a melamine resin, a polyether resin, a benzoguanamine resin, an epoxy acrylate resin, a urethane acrylate resin, and a polyester acrylate can be used.

The crosslinkable polycarbonate having an FG group as the binder resin material in the charge generation layer can be used together with the crosslinker.

Next, the charge transporting layer can be obtained by forming a layer formed by binding a charge transporting substance with a binder resin on a layer serving as a base (for example, a charge generating layer).

As a method for forming the charge transport layer, various methods such as a known method can be used. Usually, the charge transport material is crosslinked with the crosslinkable polycarbonate before crosslinking and, if necessary, with the crosslinking. A method in which a coating liquid dispersed or dissolved in an appropriate solvent together with a crosslinking agent or a radical initiator necessary for the reaction is applied onto a predetermined base layer, and a method of drying and crosslinking the crosslinkable polycarbonate is used. . The compounding ratio of the charge transporting material and the crosslinkable polycarbonate used for forming the charge transporting layer is preferably 20:80 to 80:20, more preferably 30:70 by weight.
７０70: 30.

In the formation of the charge transport layer, the above-mentioned crosslinkable polycarbonates can be used alone or as a mixture of two or more. In addition, other resins such as those mentioned as the binder resin used in the charge generation layer may be used in combination with the crosslinkable polycarbonate as long as the object of the present invention is not hindered.

As the charge transporting substance, various substances such as known substances can be used. For example, carbazole compounds, indole compounds, imidazole compounds, oxazole compounds, pyrazole compounds, oxadiazole compounds, pyrazoline compounds, thiadiazole compounds,
Aniline compounds, hydrazone compounds, aromatic amine compounds, aliphatic amine compounds, stilbene compounds, fluorenone compounds, quinone compounds, quinodimethane compounds, thiazole compounds, triazole compounds, imidazolone compounds, imidazolidine compounds, bisimidazolidine compounds, oxazolone compounds Benzothiazole compound, benzimidazole compound, quinazoline compound, benzofuran compound, acridine compound, phenazine compound, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9
-Vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole resin, or a polymer having these in the main chain or side chain is used, and preferably, a compound represented by the following general formula is used.

[0106]

Embedded image [Wherein, Ar ¹ , Ar ² and Ar ³ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, 7 carbon atoms;
To 13 substituted or unsubstituted aralkyl groups, 6 carbon atoms
To 12 substituted or unsubstituted aryl groups, polycyclic hydrocarbon groups, substituted or unsubstituted fused polycyclic hydrocarbon groups,
Represents a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, wherein Ar ¹ and Ar ² , Ar ² and Ar ^3, and Ar ³ and A
r ¹ may form a ring. ]

[0107]

Embedded image [Wherein, R ^A , R ^B , R ^C and R ^D are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkyl Amino group, carbon number 1-10
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group,
Represents a substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group, wherein A, B, C and D each independently represent 0 Is an integer of up to 5. ]

[0108]

Embedded image [Wherein, Ar ¹ and Ar ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, Substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group And Ar ¹ and Ar ² may form a ring. R
^A is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, or a heterocyclic group A group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, R ^E represents an ethylene group or an ethenylene group, and E is an integer of 0 to 4. ]

[0109]

Embedded image [Wherein, Ar ¹ and Ar ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, Substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group And Ar ¹ and Ar ² may form a ring. R
^A is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, or a heterocyclic group A group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, wherein R ^F and R ^G each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom; It is an integer of 0 to 4. ]

[0110]

Embedded image [Wherein, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted 7 to 13 carbon atoms. Aralkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, wherein Ar ⁶ and Ar ⁷ are each independently a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl compound having 6 to 12 carbon atoms. Represents a divalent residue of a polycyclic hydrocarbon, a substituted or unsubstituted fused polycyclic hydrocarbon, a heterocyclic compound, a polycyclic heterocyclic compound or a fused polycyclic heterocyclic compound, and Ar ¹
And Ar ² and Ar ³ and Ar ⁴ may form a ring. ]

[0111]

Embedded image Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently
Hydrogen atom, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon Represents a group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, wherein Ar ¹ and Ar ² and Ar ³ and Ar ⁴ May form a ring. R ^H and R ^I each independently represent a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, Or an unsubstituted alkyl group, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic ring Represents a formula hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, wherein E and F are each independently an integer of 0 to 4; ]

[0112]

Embedded image[Wherein, Ar¹, Ar^Two, Ar^ThreeAnd Ar^FourAre each independently
A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms
Killed group, substituted or unsubstituted aral having 7 to 13 carbon atoms
Killed group, substituted or unsubstituted aryl having 6 to 12 carbon atoms
Group, polycyclic hydrocarbon group, substituted or unsubstituted condensed poly
Cyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed
Represents a polycyclic heterocyclic group, Ar¹And Ar^TwoAnd Ar^ThreeWhen
Ar^FourMay form a ring. R^A, R^BAnd R^CIs German
First, a cyano group, a halogen atom, a carboxyl group,
Group, hydroxyl group, nitro group, amino group, alkyl
Amino group, arylamino group, aralkylamino group, charcoal
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, carbon
A substituted or unsubstituted aralkyl group of the formulas 7 to 13, carbon
A substituted or unsubstituted aryl group of the formulas 6 to 12, polycyclic
Hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon
Group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic
Represents a cyclic group, and E, F and G are each independently an integer of 0 to 4
It is. X¹Is -O-, -S-, -Se-, -Te-,
-CR^JR^K-, -SiR^JR^K-, -NR ^J-Or-PR^J
-(Where R^JAnd R^KAre each independently a hydrogen atom, a halogen
Atom, alkylamino group, arylamino group, arral
A substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms
An alkyl group, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms;
An aralkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms;
Reel group, polycyclic hydrocarbon group, substituted or unsubstituted condensed
Polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or
Represents a fused polycyclic heterocyclic group. ). ]

[0113]

Embedded image [Wherein, Ar ¹ and Ar ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, Substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group And Ar ¹ and Ar ² may form a ring. R
^A is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, or a heterocyclic group Represents a group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, and A is an integer of 0 to 5. ]

[0114]

Embedded image [Wherein, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted 7 to 13 carbon atoms. Aralkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, R ^A and R ^B are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group , Aralkylamino group,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, Or represents an unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, wherein Ar ¹ and Ar ² and Ar ³ and Ar ⁴ represent a ring It may be formed. F and E are each independently an integer of 0 to 4. ]

[0115]

Embedded image [In the formula, Ar ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a substituted or unsubstituted aryl having 6 to 12 carbon atoms. A group, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, R ^A , R ^B
And R ^C are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a substituted or unsubstituted group having 1 to 10 carbon atoms. Substituted alkyl group, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic carbon Represents a hydrogen group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, wherein n is 0 or 1, A, B
And C are each independently an integer of 0 to 5. ]

[0116]

Embedded image [Wherein, Ar ¹ , Ar ² and Ar ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, A substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic system represented by Formulas 6 to 12 Represents a heterocyclic group, R ^A and R ^C are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, Carbon number 1
10 to 10 substituted or unsubstituted alkyl groups, 7 to 7 carbon atoms
13 substituted or unsubstituted aralkyl groups, having 6 to 6 carbon atoms
12 substituted or unsubstituted aryl groups, polycyclic hydrocarbon groups, substituted or unsubstituted fused polycyclic hydrocarbon groups, heterocyclic groups, polycyclic heterocyclic groups or fused polycyclic heterocyclic groups R ^B ′ represents a hydrogen atom, a cyano group, a halogen atom,
Carboxyl group, acyl group, hydroxyl group, nitro group, amino group, alkylamino group, arylamino group,
Aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic carbonized A hydrogen group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, wherein n is 0 or 1,
E is an integer of 0 to 4, and H is an integer of 0 to 3. ]

[0117]

Embedded image [Wherein, Ar ¹ and Ar ² each independently represent a hydrogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, 6 to 12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group Represents a cyclic group, and Ar ¹ and Ar ² may form a ring. ]

[0118]

Embedded image [In the formula, Ar ¹ , Ar ² and Ar ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, 6 to 12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group Represents a cyclic group, and Ar ¹ and Ar ² may form a ring. ]

[0119]

Embedded image [Wherein, R ^A , R ^B , R ^C , R ^D , R ^H and R ^I each independently represent a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group An arylamino group, an aralkylamino group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms Represents a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, A, B, C , D, I and J are each independently an integer from 0 to 5. ]

[0120]

Embedded image Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently
Hydrogen atom, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group, or condensed polycyclic heterocyclic group, Ar ⁶ represents a substituted or 1 to 6 carbon atoms An unsubstituted alkylene group or a substituted or unsubstituted aryl compound having 6 to 12 carbon atoms, a polycyclic hydrocarbon, a substituted or unsubstituted fused polycyclic hydrocarbon, a heterocyclic compound, a polycyclic heterocyclic compound, or Represents a divalent residue of a condensed polycyclic heterocyclic compound, wherein Ar ¹ and Ar ² and Ar ³ and Ar ⁴ may form a ring, and n is 0 or 1. ]

[0121]

Embedded image [In the formula, R ^L , R ^M , R ^N and R ^O are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic group; Represents a ring heterocyclic group. Specifically, the following compounds are used.

[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

Embedded image The above charge transport materials can be used alone or in combination of two or more. The thickness of the charge transport layer is preferably from 5 to 100 μm, more preferably from 10 to 30 μm. If it is less than 5 μm, the initial potential will be low, and if it exceeds 100 μm, the electrophotographic properties will tend to be reduced.

A known undercoat layer, which is usually used, can be provided between the conductive substrate and the photosensitive layer. As the undercoat layer, titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide,
Fine particles such as indium oxide and silicon oxide, polyamide resin, phenol resin, casein, melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol,
Components such as a polyvinyl butyral resin can be used. These fine particles and resins can be used alone or in combination of two or more. In particular, when fine particles are used, the resin is adsorbed on the fine particles, and a smooth film can be obtained. Therefore, it is preferable to use the fine particles and the resin together. Also,
The binder resin can be used for the undercoat layer. Further, the above-mentioned crosslinkable polycarbonate having an FG group can also be used.

The thickness of the undercoat layer is usually from 0.01 to 10.
0 μm, preferably 0.01 to 1.0 μm. When the thickness is less than 0.01 μm, it is difficult to form the undercoat layer uniformly, and when the thickness exceeds 10.0 μm, the electrophotographic characteristics may be deteriorated.

In addition, a known blocking layer which is generally used can be provided between the conductive substrate and the photosensitive layer. The binder resin can be used for the blocking layer. The thickness of the blocking layer is usually 0.1.
01 to 20.0 μm, preferably 0.1 to 10.0 μm
m. If the thickness is less than 0.01 μm, it is difficult to form a blocking layer uniformly, and 20.
If it exceeds 0 μm, electrophotographic properties may be reduced.

In the organic electrophotographic photosensitive member of the present invention, a surface protective layer may be laminated on the photosensitive layer. The thickness of the surface protective layer can be 0.01 to 20 μm, and more preferably 0.1 to 10 μm. The binder resin can be used for the surface protective layer. In particular, a crosslinked product of the above-mentioned crosslinkable polycarbonate having an FG group is preferable. The surface protective layer may contain the above-mentioned charge generating substance, charge transporting substance, additive, conductive material such as metal and its oxide, nitride, salt, alloy, and carbon.

Further, the organic electrophotographic photoreceptor of the present invention includes:
Binders, plasticizers, curing catalysts, flow improvers, pinhole control agents, spectral sensitivity sensitizers for improving electrophotographic sensitivity (sensitizing dyes) ), Aside from spectral sensitivity sensitizers, various chemical substances, antioxidants, surfactants, curling prevention for the purpose of preventing increase in residual potential, decrease in charge potential, and decrease in sensitivity upon repeated use Additives such as an agent and a leveling agent can be added.

Specific examples of the binder include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, and polyisoprene. Resin, melamine resin, benzoguanamine resin, polychloroprene resin, polyacrylonitrile resin, ethyl cellulose resin, nitrocellulose resin, urea resin, phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer Coalescence, polyester carbonate resin and the like. Also, heat and / or photo-curable resins can be used. In any case, there is no particular limitation as long as the resin is electrically insulating and can form a film in a normal state.

The binder is used in an amount of 5 to 20 with respect to the charge transporting substance.
0% by weight, preferably 10 to 100% by weight
Is more preferred. If it is less than 5% by weight, the coating of the photosensitive layer tends to be non-uniform, and the image quality tends to be poor. If it exceeds 20% by weight, the sensitivity tends to decrease and the residual potential tends to increase.

Specific examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin, dimethylnaphthalene, dimethylphthalate,
Dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate, methyl naphthalene, benzophenone, polypropylene, polystyrene, various types And fluorocarbons.

Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid and the like.

Examples of the fluidity-imparting agent include Modaflow and Acronal 4F.

As the pinhole controlling agent, benzoin,
Dimethyl phthalate and the like can be mentioned.

It is preferable that the plasticizer, the curing catalyst, the flow imparting agent, and the pinhole controlling agent are used in an amount of 5% by weight or less based on the charge transporting substance.

Specific examples of the sensitizing dye include methyl violet, crystal violet, night blue,
Triphenylmethane dyes represented by Victoria Blue, etc., erythrosine, rhodamine B, rhodamine 3R,
Acridine orange, acridine dyes typified by flapeosin, methylene blue, thiazine dyes typified by methylene green, capri blue, oxazine dyes typified by Meldola blue, and other cyanine dyes,
Merocyanine dyes, styryl dyes, pyrium salt dyes, thiopyrium salt dyes and the like can be mentioned.

An electron-accepting substance can be added to the photosensitive layer for the purpose of improving sensitivity, reducing residual potential to fatigue during repeated use, and the like.

As the electron accepting substance, succinic anhydride,
Maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene , Tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, 2,3-dichloro Benzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitrotroanthraquinone, 4-
Nitrobenzophenone, 4,4-nitrobenzophenone, 4-nitrobenzalmalone dinitrile, ethyl α-cyano-β- (p-cyanophenyl) acrylate, 9-
Anthracenylmethylmalondinitrile, 1-cyano-
(P-nitrophenyl) -2- (p-chlorophenyl)
Ethylene, 2,7-dinitrofluorenone, 2,4,7
-Trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-fluorenylidene [dicyanomethylenemalononitrile], polynitro-9-fluorenylidene- [dicyanomethylenemalonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid,
3,5-dinitrobenzoic acid, pentafluorobenzoic acid,
5-nitrosalicylic acid, 3,5-dinitrosalicylic acid,
There are compounds having a high electron affinity, such as phthalic acid and melitic acid.

This electron accepting substance may be added to either the charge transport layer or the charge generation layer, and is usually 0.01 to 200% by weight, more preferably 0.1 to 200% by weight, based on the charge transport substance or the charge generation substance. ５０50% by weight.

In order to improve the surface properties, ethylene tetrafluoride resin, ethylene trifluoride chloride resin, ethylene tetrafluoride hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, An ethylene chloride resin, a copolymer thereof, or a fluorine-based graft polymer may be used.

These surface modifiers are used in an amount of 0.1 to 60% by weight, more preferably 5 to 40% by weight, based on the binder resin.
% By weight. If the amount is less than 0.1% by weight, surface modification such as abrasion resistance, surface durability and surface energy reduction is not sufficient, and if it is more than 60% by weight, electrophotographic properties may be deteriorated.

Examples of the antioxidant include a hindered phenol antioxidant, an aromatic amine antioxidant, a hindered amine antioxidant, a sulfide antioxidant, and an organic phosphoric acid antioxidant.

These antioxidants are usually used in an amount of 0.01 to 10% by weight, more preferably 0.1 to 10% by weight, based on the charge transporting substance.
2% by weight is blended.

The following are examples of hindered phenolic antioxidants.

[0189]

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[0190]

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[0191]

Embedded image Examples of the aromatic amine antioxidant include the following.

[0192]

Embedded image Examples of the hindered amine antioxidant include the following.

[0193]

Embedded image Examples of the sulfide antioxidant include the following.

[0194]

Embedded image Examples of the organic phosphoric acid antioxidant include the following.

[0195]

Embedded image Examples of the antioxidant having a hindered phenol structural unit and a hindered amine structural unit in a molecule include the following examples.

[0196]

Embedded image These additives may be used alone, or
Two or more types may be used in combination, for example, by mixing. These additives may be added to the surface protective layer, the undercoat layer, and the blocking layer.

Specific examples of the solvent used for forming the charge generation layer and the charge transport layer include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, and ketones such as acetone, methyl ethyl ketone and cyclohexanone. Alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate and ethyl cellosolve, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and tetrachloroethane, ethers such as tetrahydrofuran and dioxane, dimethylformamide, dimethyl sulfoxide and diethyl Formamide and the like can be mentioned.

These solvents may be used alone or in combination of two or more.

As a method for forming the charge transport layer, a solution prepared by dispersing or dissolving the above-described charge transport material, additive, crosslinkable polycarbonate, and, if necessary, a crosslinking agent or a radical initiator in a solvent is applied to a predetermined base. Substrate, dip coating method, electrostatic coating method, powder coating method, spray coating method, roll coating method, applicator coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating on the layer Coating using a coating method such as construction method, doctor blade coating method, wire bar coating method, knife coater coating method, attritor coating method, spinner coating method, bead coating method, blade coating method, curtain coating method, drying and drying It can be formed by performing a crosslinking reaction of a crosslinkable polycarbonate.

As the method of dispersing or dissolving, a ball mill, ultrasonic wave, paint shaker, red devil, sand mill, mixer, attritor and the like can be used.

The crosslinking reaction can be carried out under any pressure from reduced pressure to increased pressure, but is preferably carried out under reduced pressure or normal pressure. The conditions for the crosslinking reaction are as described above.

The photosensitive layer of the single-layer type organic electrophotographic photosensitive member is formed by the above-mentioned charge generating substance, charge transporting substance, additive, crosslinkable polycarbonate as a binder resin material, and, if necessary, a crosslinker or a radical initiator. Is dispersed or dissolved in a solvent, and the resulting solution is applied onto a substrate serving as a predetermined base, followed by drying and crosslinking of the crosslinkable resin.
The coating method, crosslinking method, additives, etc. are the same as described above. Further, a surface protective layer, an undercoat layer, and a blocking layer may be provided in the same manner as described above.

The thickness of the single-layer type photosensitive member is usually 5 to 100 μm.
Is preferable, and 8 to 50 μm is more preferable. If it is less than 5 μm, the initial potential tends to be low, and if it exceeds 100 μm, the electrophotographic properties tend to be reduced.

The ratio by weight of the charge generating substance: crosslinkable polycarbonate used in the production of the single-layer type organic electrophotographic photosensitive member is preferably from 1:99 to 30:70, and more preferably from 3:97 to 15:85. . The ratio by weight of the charge transport material: crosslinkable polycarbonate is preferably 10:90 to 80:20, and more preferably 30:90.
70 to 70:30.

Further, other resins can be used in combination with the above-mentioned crosslinkable polycarbonate within a range not to impair the achievement of the object of the present invention.

A resin other than the above-mentioned crosslinkable polycarbonate having an FG group may be used as the binder resin in the photosensitive layer, and the above crosslinkable polycarbonate may be used only for forming the surface protective layer.

As the method for forming the surface protective layer, various methods such as a known method can be used. Usually, the above-mentioned crosslinkable polycarbonate before crosslinking and, if necessary,
Crosslinking agent or radical initiator required for the crosslinking reaction, additives,
A method in which a coating solution dispersed or dissolved in a suitable solvent together with a conductive material or the like is applied on the photosensitive layer, and then dried and crosslinked with the crosslinkable polycarbonate is used. In the formation of the surface protective layer, the above-mentioned crosslinkable polycarbonates can be used alone or as a mixture of two or more. In addition, other resins such as those mentioned as the binder resin used in the charge generation layer may be used in combination with the crosslinkable polycarbonate as long as the object of the present invention is not hindered. The preferred thickness of the surface protective layer is as described above, and the solvent, coating method, curing method, and the like used for forming the surface protective layer are the same as those described above for the method of forming the charge transport layer.

The thus obtained organic electrophotographic photoreceptor of the present invention has high surface hardness and abrasion resistance, and maintains excellent electrophotographic properties and toner filming resistance over a long period of time. The present invention can be suitably used in various electrophotographic fields such as a copying machine (monochrome, multicolor, full color; analog, digital), a printer (laser, LED, liquid crystal shutter), a facsimile, and a plate making machine.

In using the organic electrophotographic photoreceptor of the present invention, a corona discharge (corotron, scotron), contact charging (charging roll, charging brush) or the like is used as a charger. The exposure is performed by a halogen lamp, a fluorescent lamp, a laser (semiconductor, He-Ne), an LED, and a photoconductor internal exposure system. As the developing process, a dry developing system such as a cascade developing, a two-component magnetic brush developing, a one-component insulating toner developing, a one-component conductive toner developing, or a wet developing system is used. In the transfer step, an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method is used. For fixing, heat roller fixing, radiant flash fixing, oven fixing, pressure fixing and the like are used. For cleaning and static elimination, a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, and the like are used.

[0210]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Synthesis Example 1 (Synthesis of biphenyl-type crosslinkable polycarbonate (PC-1)) 5% Pd / C (100 g) was added to 1 liter of water, and water (1 liter) in which NaOH (200 g) was dissolved.
Was added. One liter of methanol in which 4-bromo-2-phenylphenol (456 g, 1.83 mol) was dissolved was added thereto, and the mixture was refluxed for 3 hours. After methanol was removed by distillation, the catalyst was filtered, neutralized with hydrochloric acid, and extracted with methylene chloride. The organic layer was washed with water, concentrated, and distilled at about 330 ° C. in a metal bath. This was recrystallized from a mixed solution of toluene: cyclohexane-1: 3 (weight ratio) to obtain a precursor of the compound of the following formula A (66 g, yield 2).
1%) The obtained precursor was dissolved in a methanol solution (500 ml) of NaOH (30 g), and allyl bromide (50.4%) was dissolved.
After slowly adding g), the mixture was refluxed for 5 hours. After the obtained solution was dried under reduced pressure, it was redissolved in methylene chloride,
After washing with 0.1 N hydrochloric acid, it was washed twice with water. After the organic layer was separated and dried over magnesium sulfate, the solvent was distilled off, and the mixture was directly heated at 200 ° C. for 5 hours under a nitrogen stream to obtain a compound of the formula A (65 g).

[0212]

Embedded image 2,2-bis (4-hydroxyphenyl) propane 74
g in 550 ml of a 6% by weight aqueous sodium hydroxide solution
Phosgene gas was added to the solution under cooling while stirring and mixing the solution dissolved in methylene chloride with 250 ml of methylene chloride.
Blowing was performed at a rate of 0 ml / min for 15 minutes. Then, the reaction solution was allowed to stand to separate an organic layer, and bisphenol A (2,2-bis (4
-Hydroxyphenyl) propane) in methylene chloride was obtained.

Methylene chloride was added to a methylene chloride solution of the above oligomer to make the total amount 450 ml, and then 8% by weight.
Of a compound of the formula A and p.
3.0 g of -tert-butylphenol were added. Then, while vigorously stirring the mixture, 2 ml of a 7% by weight aqueous solution of triethylamine was added as a catalyst, and
The reaction was carried out at 1.5 ° C. under stirring for 1.5 hours. After completion of the reaction, the reaction product was diluted with 1 liter of methylene chloride, and then washed twice with 1.5 liter of water. The resulting solution was ice-bathed and 51.6 g of metachloroperbenzoic acid was added in several portions and added slowly. After the entire amount was added, the temperature was returned to room temperature, and stirring was continued for 24 hours. Subsequently, this was washed with a 0.01 N NaOH aqueous solution, washed once with 1 liter of 0.01 N hydrochloric acid and twice with 1 liter of water, and the organic layer was poured into methanol. And dried to obtain 103 g of polycarbonate (PC-1).

The reduced viscosity [η _sp / c] at 20 ° C. of a solution of the thus obtained polycarbonate having a concentration of 0.5 g / dl in methylene chloride as a solvent was 0.75 dl.
/ G. The reduced viscosity was measured using an automatic viscosity measuring machine VMR-042 manufactured by Rigosha Co., Ltd. with an automatic viscosity Ubbelohde improved viscometer (RM type).

The obtained polycarbonate (PC-1)
The result of IR spectrum analysis was 3030 cm^-1, 159
0cm^-1, 830cm^-1Absorption of benzene ring, 1730
cm ^-1Absorption by carbonate group, 1130cm^-1To
Absorption derived from epoxy group is observed and carbonate bond
And an epoxy group. The obtained po
The copolymer composition of the carbonate (PC-1) is¹H-NM
Determined by R analysis. Based on these analysis results,
-Carbonate (PC-1) has the following repeating unit
It was found to be contained in the composition.

[0216]

Embedded image Synthesis Example 2 (Synthesis of naphthalene-type crosslinkable polycarbonate (PC-2))

[0219]

Embedded image Polycarbonate (PC-2) having the following structure by the same operation as in Synthesis Example 1 except that the compound was changed to 25.2 g, and the reaction with metachloroperbenzoic acid was not performed and the washing with an aqueous NaOH solution was not performed. ([Η _sp /c]=0.77d
1 / g) 102 g were obtained.

In the synthesis of the compound of formula A, 2,7-naphthalenediol (manufactured by Sugai Chemical Industry Co., Ltd.) was used in place of the precursor obtained in the first-stage reaction in the synthesis of the compound of formula A. ) Except that 32 g was used.

IR of this polycarbonate (PC-2)
The result of the spectrum analysis was 3030 cm ⁻¹ , 1590 c
m ^-1, the absorption of the benzene ring to 830 cm ^-1, 1730 cm
⁻¹ , absorption by carbonate group, 910 cm ⁻¹ , 990
An absorption derived from a vinyl group was observed at cm ⁻¹ , and it was confirmed that the resin had a carbonate bond and an epoxy group. The copolymer composition of the obtained polycarbonate (PC-2) was ¹ H
-Determined by NMR analysis. From these analysis results,
Polycarbonate (PC-2) was found to contain the following repeating units in the following composition.

[0220]

Embedded image Synthesis Example 3 (Synthesis of biphenyl-type crosslinkable polycarbonate (PC-3)) In Synthesis Example 1, 22.7 g of the compound of formula A was 3,3'-dihydroxy-4,4'-diaminobiphenyl.
To react with metachloroperbenzoic acid,
A polycarbonate (PC having the following structure) was prepared in the same manner as in Synthesis Example 1 except that washing with an aOH aqueous solution was not performed.
-3) ([η _sp /c]=0.77 dl / g) 102 g was obtained. The polycarbonate (PC-3) results of IR spectral analysis of, 3030cm ^-1, 1590cm ^-1,
830 cm ^-1 to the absorption of the benzene ring, the absorption due to carbonate groups in the 1730 cm ^-1, the absorption was observed to be derived from the amino group 3300 cm ^-1, to have a carbonate bond and an amino group was observed. The copolymer composition of the obtained polycarbonate (PC-3) was determined by ¹ H-NMR analysis. From these analysis results, the polycarbonate (P
C-3) was found to contain the following repeating units in the following composition.

[0221]

Embedded imageSynthesis Example 4 (Naphthalene-type crosslinkable polycarbonate (PC-4)
Synthesis) In Synthesis Example 1, the compound of the formula A is replaced with the compound of the formula B
The same operation as in Synthesis Example 1 was carried out except that the amount was changed to 25.2 g.
Polycarbonate (PC-4) ([η
_sp/C]=0.79 dl / g). This port
Results of IR spectrum analysis of carbonate (PC-4)
Fruit is 3030cm^-1, 1590cm^-1, 830cm^-1
Benzene ring absorption, 1730cm^-1Carbonate group
Absorption by 1130cm^-1Absorption due to epoxy group
It has a carbonate bond and an epoxy group.
It was recognized that. The obtained polycarbonate (PC-
The copolymer composition of 4) is¹Determined by 1 H-NMR analysis.
From these analysis results, polycarbonate (PC-4)
Contains the following repeating units in the following composition.
won.

[0222]

Embedded image Example 1 (Biphenyl type-ion crosslinked type) 1-phenyl-1,2,3,4-tetrahydroquinoline-6-carboxaldehyde-1 ', 1'-diphenylhydrazone (C-1) was used as a charge transport material. Using (PC-1) as a binder resin material and xylylenediamine (MXDA) as a crosslinking agent, (C-1): (PC-1): MX
A solution of DA: methylene chloride = 1: 1: 0.2: 8 (weight ratio) was prepared and used as a coating liquid. This coating solution did not show any white turbidity or gel formation even after being left for one month.

Aluminum conductive substrate (50 mm × 5
A dispersion of oxotitanium phthalocyanine: butyral resin: methylene chloride = 1: 1: 38 (weight ratio) is applied on a flat plate of 0 mm and a cylindrical type of φ168 mm × 360 mm by dip coating. A layer of phthalocyanine (about 0.5 μm) was formed as a charge generation layer. The above-mentioned coating solution is applied on the charge generation layer by a dip coating method, and after drying, a crosslinking reaction is performed at 150 ° C. for 10 hours to form a charge transport layer of about 20 μm. The body was made. The charge transport layer did not crystallize during the process from coating to crosslinking.

The evaluation of the center line average roughness Ra value and the electrophotographic characteristics of the surface of the obtained organic electrophotographic photosensitive member after the deterioration test was performed using the above-mentioned flat organic electrophotographic photosensitive member.

The deterioration test was performed using a Suga abrasion tester NUS-IS.
This was performed using an O-3 type (manufactured by Suga Test Instruments Co., Ltd.). The test conditions were as follows: A sample of the laminated organic electrophotographic photoreceptor was reciprocated 2000 times on abrasion test paper (Al ₂ O ₃ , 3 μm polishing paper manufactured by Suga Test Instruments Co., Ltd.) with a load of 500 g, Measurement of the weight loss amount and the center line average roughness Ra value of the surface (based on JIS-B-0601, manufactured by Tokyo Seimitsu Co., Ltd.
Using a surface roughness profile measuring device Surfcom 575A) and electrophotographic characteristics before and after the deterioration test (Electrostatic charging tester EPA)
Using -8100 (manufactured by Kawaguchi Electric Works), -6
It was evaluated by measuring the initial surface potential (V ₀ ), the residual potential (V _R ) after 5 seconds of light irradiation (10 Lux), and the half-life exposure (E _1/2 ) by performing a kV corona discharge. .
The results are shown in Tables 1 and 2.

The evaluation of the deterioration of the toner filming resistance when the obtained organic electrophotographic photosensitive member was repeatedly used in the actual machine was performed using the cylindrical organic electrophotographic photosensitive member.

The evaluation was performed using a commercially available copying machine (Carlson system,
Use of organic electrophotographic photoreceptor, use of cylindrical drum (φ168
mm × 360 mm, made of aluminum), corona charging method (voltage -800 V), blade cleaning method (urethane blade, blade pressure 1 kg / cm ² ), two-component developer (using styrene acrylic toner, ferrite carrier)) Using a tester equipped with the above-mentioned organic electrophotographic photosensitive member, copying of the test pattern was repeated up to 30,000 sheets in an A4 size portrait mode at 22 to 27 ° C. and 10 to 30% humidity, and the obtained organic electrophotograph was obtained. A black spot visible on the photoconductor (toner filming has occurred and toner components adhered to the organic electrophotographic photoconductor) is 10 mm × 10 m
The number of m in m was observed and evaluated. Table 3 shows the obtained results.

Example 2 (Naphthalene Type-Radical Crosslinking Type) MXD was performed using (PC-2) instead of (PC-1) used in Example 1.
Azobisisobutyronitrile (AIBN) instead of A
A laminated organic electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the conditions after drying were changed to 120 ° C. for 1 hour.

With respect to the obtained organic electrophotographic photosensitive member, a deterioration test, an electrophotographic characteristic test before and after the deterioration test, and a toner filming resistance test were performed in the same manner as in Example 1. Table 3 shows the results.

[0230] The coating liquid prepared in this example did not show white turbidity or gelation even after being left for one month.

Example 3 (Biphenyl type-ion crosslinked type) Using (PC-3) instead of (PC-1) used in Example 1, MXDA
Was replaced with bisphenol A type epoxy resin (epoxy equivalent: 1300), and a laminated organic electrophotographic photoreceptor was produced in the same material mixing ratio and operation as in Example 1.

With respect to the obtained organic electrophotographic photosensitive member, a deterioration test, an electrophotographic characteristic test before and after the deterioration test, and a toner filming resistance test were performed in the same manner as in Example 1. Table 3 shows the results.

The coating liquid prepared in this example did not show any white turbidity or gel formation even after being left for one month.

Example 4 (Naphthalene type-ion cross-linking type) Except that (PC-4) was used instead of (PC-1) used in Example 1,
A laminated organic electrophotographic photoreceptor was produced in the same material mixing ratio and operation as in Example 1.

The obtained organic electrophotographic photosensitive member was subjected to a deterioration test, an electrophotographic characteristic test before and after the deterioration test, and a toner filming resistance test in the same manner as in Example 1. Table 3 shows the results.

The coating liquid prepared in this example did not show any cloudiness or generation of gel after being left for one month.

Comparative Example 1 Polycarbonate (PC-5) was synthesized by the following procedure according to the method described in JP-A-4-291348 until the production of a polycarbonate before crosslinking.

While flowing dry nitrogen gas into a three-necked round bottom flask equipped with a stirrer, thermometer, gas inlet tube and reflux condenser, a 48.5% by weight aqueous sodium hydroxide solution 5 was added.
3.7 parts, 230.8 parts of water, 31.4 parts of 3,3'-diallylbisphenol A, and 27.3 parts of bisphenol Z were charged and dissolved. The solution was cooled to 20 ° C. in an ice bath,
With stirring, 26.2 parts of phosgene gas were gradually introduced over 1 hour. Thereafter, 8.4 parts of a 48.5% by weight aqueous sodium hydroxide solution were added, and pt was added as a reaction terminator.
After adding 0.61 part of tert-butylphenol, 30
The polymerization reaction was continued at 1 ° C. for 1 hour. After the reaction yield, the methylene chloride layer was separated and acidified with hydrochloric acid, and then washed repeatedly with water to remove dissolved salts. Thereafter, the methylene chloride was evaporated to obtain a solid. The obtained solid had the following repeating units and copolymer composition.

[0239]

Embedded image (PC-5): (C-1): pentaerythritol tetrakis (3-mercaptopropionate) (crosslinking agent):
Irgacure 907 (crosslinking agent: Ciba-Geigy): methylene chloride = 1: 1: 0.1: 0.01: 8
(Weight ratio) was prepared as a coating liquid for forming a charge transport layer. Hereinafter, the same operation as in Example 1 was performed until drying after application of the coating liquid. After drying, the mixture was irradiated with a high-pressure mercury lamp having an irradiation energy of 80 w / cm ² for 5 seconds to produce a crosslinked laminated organic electrophotographic photosensitive member.

The obtained organic electrophotographic photosensitive member was subjected to a deterioration test, an electrophotographic characteristic test before and after the deterioration test, and a toner filming resistance test in the same manner as in Example 1. Table 3 shows the results.

[0241] The coating liquid prepared in this example did not show any white turbidity or gel formation even after being left for one month.

[0242]

[Table 1]

[0243]

[Table 2]

[0244]

[Table 3]

[0245]

According to the present invention, the surface of the photosensitive layer of the organic electrophotographic photosensitive member of the present invention is formed of a material having not only a high surface hardness and excellent abrasion resistance, but also a very small increase in surface roughness after abrasion. Therefore, excellent electrophotographic characteristics and toner filming resistance are maintained over a long period of time.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masami Kanamaru 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (5)

[Claims] 1. An organic electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate has a center line average roughness Ra value of 0.01.
The surface is ～0.15Myuemu, abrasive particles Al ₂ O ₃ 3μ
When the polishing test is performed by reciprocating 2,000 times of abrasive paper 2000 times with a load of 500 g, the center line average roughness Ra after the polishing test is obtained.
An organic electrophotographic photoreceptor having a surface formed of a substance having a value of 0.17 μm or less. 2. The organic electrophotographic photosensitive member according to claim 1, wherein the substance forming the photosensitive layer contains a crosslinked polycarbonate as a binder resin. 3. The organic electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a surface protective layer containing a crosslinked polycarbonate. 4. A crosslinked polycarbonate comprising a repeating unit (I) represented by the following general formula (I) and a repeating unit (II) represented by the following general formula (II), wherein 0 2 of a solution having a concentration of 0.5 g / dl
The organic electrophotographic photoreceptor according to claim 2 or 3, which is a crosslinked product of a crosslinkable polycarbonate having a reduced viscosity at 0 ° C of 0.5 to 20.0 dl / g. Embedded image [Wherein, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 11 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. , Y is a single bond or -O-, -CO-, -S-,-
SO—, —SO ₂ —, —CR ³ R ⁴ — (R ³ and R ⁴ are each independently a hydrogen atom, a trifluoromethyl group,
And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ), 1,1- having 5 to 11 carbon atoms
A cycloalkylidene group, an α, ω-alkylene group having 2 to 12 carbon atoms, or a compound represented by the following formula (a): (Wherein c is an integer of 0 to 4), a and b each independently represent an integer of 0 to 4,
⁵ and R ⁶ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms,
To 12 substituted or unsubstituted aryl groups or 6 carbon atoms
Represents 12 to 12 substituted or unsubstituted aryloxy groups, and FG is (In the formula, h represents an integer of 0 to 4, and R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Represents.)
And d, e, f and g each independently represent an integer of 0 to 4, provided that d + e = 1 to 8, d + f = 0 to 4, e + g =
0 to 4. ] 5. A crosslinked polycarbonate comprising a repeating unit (I) represented by the following general formula (I) and a repeating unit (II) represented by the following general formula (III), wherein methylene chloride is used as a solvent. 5 g / dl concentration solution 2
The organic electrophotographic photoreceptor according to claim 2 or 3, which is a crosslinked product of a crosslinkable polycarbonate having a reduced viscosity at 0 ° C of 0.1 to 20.0 dl / g. Embedded image [Wherein, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 11 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. , Y is a single bond or -O-, -CO-, -S-,-
SO—, —SO ₂ —, —CR ³ R ⁴ — (R ³ and R ⁴ are each independently a hydrogen atom, a trifluoromethyl group,
And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ), 1,1- having 5 to 11 carbon atoms
A cycloalkylidene group, an α, ω-alkylene group having 2 to 12 carbon atoms or the following formula (a): (Wherein c is an integer of 0 to 4), a and b each independently represent an integer of 0 to 4,
⁹ and R ¹⁰ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a C 6 to C 12 FG represents a substituted or unsubstituted aryloxy group, and FG is (In the formula, h represents an integer of 0 to 4, and R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Represents.)
And i, j, k and l each independently represent an integer of 0 to 3, provided that i + j = 1 to 6, i + k = 0 to 3, and j + 1 =
0 to 3. ]