JP2000352830A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly sensitive and durable electrophotographic photosensitive member containing an aromatic polycarbonate resin having a charge transporting ability in a photosensitive layer. SOLUTION: A photosensitive layer containing, as an active ingredient, a polycarbonate resin containing at least a structural unit represented by the following general formula (b) or (c) is provided on a conductive support. Photoconductor. Embedded image (In the formula, Ar ¹ , Ar ² , and Ar ³ represent a substituted or unsubstituted arylene group. R ³ and R ⁴ are the same or different acyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups. Represents the following.) (In the formula, Ar ¹ , Ar ² , Ar ³ , R ³ , and R ⁴ are the same as defined above.)

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 a highly sensitive and highly durable electrophotographic photoreceptor containing an aromatic polycarbonate resin having a charge transporting ability in a photosensitive layer.

[0002]

2. Description of the Related Art In recent years, organic photoconductors (OPCs) have been used in copiers,
Often used in printers. As a typical configuration example of an organic photoreceptor, a charge generation layer (CG) is formed on a conductive substrate.
L) and a laminated photoreceptor in which a charge transport layer (CTL) is sequentially laminated. The charge transport layer is made of a low molecular charge transport material (CT
M) and a binder resin. However,
The inclusion of the low-molecular charge transport material lowers the mechanical strength inherent in the binder resin, which causes abrasion, scratches, cracks, etc. of the photoreceptor, and impairs the durability of the photoreceptor. I have.

As a photoconductive polymer material, vinyl polymers such as polyvinyl anthracene, polyvinyl pyrene, and poly-N-vinyl carbazole have been studied as charge transfer complex type photoconductors in the past, but they are satisfactory in terms of photosensitivity. I couldn't do it. On the other hand, in order to improve the above-mentioned drawbacks of the laminated photoreceptor, studies have been made on a polymer material having a charge transporting ability. For example, an acrylic resin having a triphenylamine structure (M. Stolka et al. J.
Polym. Sci. , Vol 21, 969 (198
3)), a vinyl polymer having a hydrazone structure (Jap
an HardCopy '89P. 67) and polycarbonate resins having a triarylamine structure (U.S. Pat. Nos. 4,801,517, 4,806,443, 4,806,444, 4,937,165, and 4,959, U.S. Pat. Nos. 288, 5,030,532, 5,034,296, 5,080,989, JP-A-64-9964, and JP-A-3-22522.
JP-A-2-304456, JP-A-4-11627
JP-A-4-175337, JP-A-4-18371
JP-A-4-31404, JP-A-4-13306
No. 5, each publication), but has not been put to practical use.

Further, M. A. Have compared the low-dispersion type and the polymerized polycarbonate using a tetraarylbenzidine derivative as a model compound, and have found that the polymer system has an order of magnitude lower drift mobility (Physical). Review B46
6705 (1992). Although the cause of this is not clear, it suggests that there is a problem in electrical characteristics such as sensitivity and residual potential, although the mechanical strength is improved by polymerizing.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and has been achieved by using an aromatic polycarbonate resin having a charge transporting ability.
It is an object of the present invention to provide a highly sensitive and highly durable electrophotographic photosensitive member.

As a method for producing an aromatic polycarbonate resin, an interfacial polymerization method is widely used industrially. However, it is necessary to completely remove impurities such as salts and alkalis from a polymer solution. A considerable amount of technology is required for industrial implementation, and in order to obtain a high-purity product required as the charge transporting polymer material according to the present invention, more advanced technology is required. JP-A-8-261983, JP-A-9-151248, and JP-A-9-272735 have proposed a solution polymerization method using a chloroformate. However, since the synthesis of the chloroformate is required, the reaction is carried out. Lack of diversity. In addition, this method has another problem that it is difficult to obtain a high molecular weight polymer. Therefore, the present invention is that the charge transporting aromatic polycarbonate resin is produced by a solution polymerization method which can be produced using a simple apparatus at a room temperature, in a uniform liquid phase, and using a simple apparatus. This is one of the purposes.

Also, diol compounds having an ester bond are difficult to obtain the desired high molecular weight polymer by the interfacial polymerization method because of the hydrolysis. In the present invention, it is another object of the present invention to easily obtain a high molecular weight polymer by employing a solution polymerization method.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin containing a specific structural unit obtained by a solution polymerization method on a conductive support. It has been found that the above-mentioned problem can be solved by providing the above, and the present invention has been achieved.

That is, the present invention provides the following (1) to (6). (1) A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin obtained by solution polymerization of a diphenol compound having a triarylamine structure and a diol compound represented by the following general formula (a) is provided. A photoconductor for electrophotography, characterized by:

[0010]

Embedded image (Wherein R ¹ and R ² are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, Y is -COO-, or the following formula

Embedded image And Z represents a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group. )

(2) A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin in which the diphenol compound having a triarylamine structure in (1) is a diphenol compound represented by the following general formula (b): A photoconductor for electrophotography, comprising:

[0012]

Embedded image (In the formula, Ar ¹ , Ar ² , and Ar ³ represent a substituted or unsubstituted arylene group. R ³ and R ⁴ are the same or different acyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups. Represents.)

(3) A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin in which the diphenol compound having a triarylamine structure in (1) is a diphenol compound represented by the following general formula (c): A photoconductor for electrophotography, comprising:

[0014]

Embedded image (In the formula, Ar ¹ , Ar ² , Ar ³ , R ³ , and R ⁴ are the same as defined above.)

(4) A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin represented by the following general formula (d) obtained by solution polymerization of the above general formulas (a) and (b). A photoconductor for electrophotography, comprising:

[0016]

Embedded image (Wherein, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ , R ⁴ ,
a and b are the same as defined above. k is an integer of 5 to 5000, j is an integer of 5 to 5000, and 0 <k / (k +
j) ≦ 1)

(5) A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin represented by the following general formula (e) obtained by solution polymerization of the above general formulas (a) and (c). A photoconductor for electrophotography, comprising:

[0018]

Embedded image (Wherein, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ , R ⁴ ,
a and b are the same as defined above. k is an integer of 5 to 5000, j is an integer of 5 to 5000, and 0 <k / (k +
j) ≦ 1)

(6) In the solution polymerization of (1), dehydrated pyridine is used as a deoxidizing agent, and its ratio in a reaction solvent is 5 to 5.
An electrophotographic photoconductor comprising a photosensitive layer containing an aromatic polycarbonate resin produced at 100% by volume as an active ingredient.

As described above, the electrophotographic photoreceptor of the present invention preferably has, as a preferred embodiment, a diphenol represented by the general formula (b) or (c) having a charge transporting ability in a photosensitive layer. It contains a copolymerized polycarbonate resin using the diol represented by the general formula (a) for imparting mechanical properties, and these aromatic polycarbonate resins have charge transporting ability and high mechanical properties. Since the photoreceptor has high strength, the photoreceptor has high sensitivity and high durability.

In another preferred embodiment, the electrophotographic photoreceptor of the present invention comprises, as described above, a polycarbonate containing at least the structural units represented by formulas (d) and (e) in the photosensitive layer. A photosensitive layer containing a resin as an active ingredient is provided. These polycarbonate resins are produced by the following method.

The aromatic polycarbonate resin used in the present invention is obtained by dissolving a diol in a solvent, adding a deoxidizing agent,
This is obtained by solution polymerization in which a carbonyl halide compound is added. As the carbonyl halide compound, instead of phosgene, trichloromethylchloroformate which is a dimer of phosgene and bis (trichloromethyl) carbonate which is a trimer of phosgene are also useful, and halogens derived from halogens other than chlorine are also useful. Also useful are carbonyl iodide compounds such as carbonyl bromide, carbonyl iodide, carbonyl fluoride. This production method is described, for example, in a polycarbonate resin handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun). Tertiary amines such as trimethylamine, triethylamine, tripropylamine and pyridine are used as deacidifiers. Examples of the solvent used in the reaction include, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene, and chloroform; and cyclic ether solvents such as tetrahydrofuran and dioxane; and hydrocarbon solvents such as toluene and xylene. And pyridine are preferred. When pyridine is used as a deoxidizing agent, pyridine forms an adduct with phosgene, which is more reactive with bisphenol than phosgene itself. When the phosgene-pyridine adduct is present in excess relative to bisphenol, both ends of the polymer form a chloroformate-pyridine adduct.In such a case, the addition of bisphenol in an amount equivalent to the molar amount thereof results in a decrease in molecular weight. Strictly doubled. Strictly stoichiometric amounts of bisphenol, phosgene and pyridine must be used to produce high molecular weight polycarbonates, but phosgene is usually slightly more than stoichiometric and pyridine more than stoichiometric for phosgene. It is most preferable to use it in a slightly excessive amount from the viewpoint of providing a high yield. The molecular weight of the produced polycarbonate is mainly governed by the reaction temperature, the amount of pyridine, the amount of phosgene, the rate of phosgene addition, the amount of the molecular weight modifier added, and the like. In the solution polymerization of the present invention, dehydrated pyridine is used as a deoxidizing agent, and its proportion in the reaction solvent is 5 to 100% by volume, preferably 30 to 50% by volume.
It is. In the solution method, since the presence of water decomposes the phosgene-pyridine adduct or the chloroformate-pyridine adduct at the molecular terminal, it must be carried out in a completely dehydrated non-aqueous system. In this manner, the aromatic polycarbonate resin having the charge transporting ability represented by the general formula (d) can be produced, and the diphenol compound having the charge transporting ability represented by the general formula (b) or (c) and the general formula The ratio with the diol represented by (a) can be selected from a wide range depending on desired characteristics. By selecting an appropriate polymerization operation, a random copolymer, an alternating copolymer, a block copolymer, a random alternating copolymer, a random block copolymer, and the like can be obtained. Also, a random block copolymer can be obtained by adding several kinds of diphenols during the reaction.

In the above polymerization operation, it is desirable to use a terminal terminator as a molecular weight regulator in order to control the molecular weight. Therefore, the terminal of the polycarbonate resin used in the present invention has a substituent based on the terminator. They may be combined. The terminating agent used is a monovalent aromatic hydroxy compound, a haloformate derivative of a monovalent aromatic hydroxy compound, a monovalent carboxylic acid or a halide derivative of a monovalent carboxylic acid. Monovalent aromatic hydroxy compounds include, for example, phenol, p-cresol, o-ethylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-
Cumylphenol, p-cyclohexylphenol, p
Octylphenol, p-nonylphenol, 2,4
-Xylenol, p-methoxyphenol, p-hexyloxyphenol, p-decyloxyphenol, o
-Chlorophenol, m-chlorophenol, p-chlorophenol, p-bromophenol, pentabromophenol, pentachlorophenol, p-phenylphenol, p-isopropenylphenol, 2,4-di (1'-methyl-1 '-Phenylethyl) phenol,
β-naphthol, α-naphthol, p- (2 ′, 4 ′,
4 "-trimethylchromanyl) phenol, 2- (4 '
Phenols such as methoxyphenyl) -2- (4 "-hydroxyphenyl) propane or alkali metal salts and alkaline earth metal salts thereof. The haloformate derivative of a monovalent aromatic hydroxy compound is as described above.
And haloformate derivatives of monovalent aromatic hydroxy compounds.

The monovalent carboxylic acid is, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, cabrylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid, 3,3-dimethylbutyric acid , 4-methylvaleric acid, 3,
3-dimethylvaleric acid, 4-methylcaproic acid, 3,5-
Dimethylcaproic acid, fatty acids such as phenoxyacetic acid or their alkali metal salts and alkaline earth metal salts,
Benzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p-butoxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid, p-chlorobenzoic acid, etc. Acids or their alkali metal and alkaline earth metal salts. Examples of the monovalent carboxylic acid halide derivative include the above-described monovalent carboxylic acid halide derivatives. These terminal blocking agents may be used alone or in combination of two or more. The terminal blocking agent is preferably a monovalent aromatic hydroxy compound, more preferably phenol, p-tert.
-Butylphenol or p-cumylphenol. The preferred molecular weight of the polycarbonate resin of the present invention is 1,000 to 50,000 in terms of polystyrene equivalent number average molecular weight.
0, more preferably 10,000 to 200,000. The reaction temperature is usually 0 to 40 ° C, and the reaction time is several minutes to 5 minutes.
Time.

In addition, a small amount of a branching agent can be added during the polymerization in order to improve the mechanical properties. The branching agent used is a compound having three or more (same or different) reactive groups selected from an aromatic hydroxy group, a haloformate group, a carboxylic acid group, a carboxylic acid halide group or an active halogen atom. is there. Specific examples of the branching agent include phloroglucinol, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene,
4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) heptane, 1,3,5-tris (4'-
Hydroxyphenyl) benzene, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-hydroxyphenyl) propane, α, α,
α'-tris (4'-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 2,4-bis [α-methyl-α- (4'-hydroxyphenyl) ethyl] phenol, 2- (4'hydroxy Phenyl) -2-
(2 ″, 4 ″ -dihydroxyphenyl) propane, tris (4-hydroxyphenyl) phosphine, 1,1,
4,4-tetrakis (4'-hydroxyphenyl) cyclohexane, 2,2-bis [4'-4'-bis- (4 "
-Hydroxyphenyl) cyclohexyl] propane,
α, α, α ′, α′-tetrakis (4′-hydroxyphenyl) -1,4-diethylbenzene, 2,2,5,5
-Tetrakis (4'-hydroxyphenyl) hexane,
1,1,2,3-tetrakis (4'-hydroxyphenyl) propane, 1,4-bis (4 ', 4 "-dihydroxytriphenylmethyl) benzene, 3,3'5,5'-
Tetrahydroxydiphenyl ether, 3,5-dihydroxybenzoic acid, 3,5-bis (chlorocarbonyloxy) benzoic acid, 4-hydroxyisophthalic acid, 4-chlorocarbonyloxyisophthalic acid, 5-hydroxyphthalic acid, 5-chlorocarbonyloxy Phthalic acid, trimesic acid trichloride, cyanuric chloride and the like.
These branching agents may be used alone or in combination.

If necessary, additives such as an antioxidant, a light stabilizer, a heat stabilizer, a lubricant, and a plasticizer can be added to the aromatic polycarbonate resin produced according to the above method.

Next, the general formulas (b), (c), (d) and (e), which are the main structural units of the present invention, will be described in more detail.

The general formulas (b), (c), (d),
In (e), R ³ and R ⁴ represent the same or different acyl groups, substituted or unsubstituted alkyl groups, and substituted or unsubstituted aryl groups.

Examples of the substituted or unsubstituted alkyl group for R ³ and R ⁴ include the following.

A linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups may further be a fluorine atom, a cyano group, a phenyl group or a halogen atom or a carbon atom having 1 to 5 carbon atoms.
It may contain a phenyl group substituted with 5 linear or branched alkyl groups. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group,
s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-
Examples thereof include a chlorobenzyl group and a 4-methylbenzyl group.

Examples of the substituted or unsubstituted aryl group for R ³ and R ⁴ include the following.

Phenyl, naphthyl, biphenylyl, terphenylyl, pyrenyl, fluorenyl,
9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, thienyl group, benzothienyl group , Furyl group, benzofuranyl group,
A carbazolyl group, a pyridinyl group, a pyrrolidyl group, an oxazolyl group, and the like.These include the above-mentioned substituted or unsubstituted alkyl group, the above-described substituted or unsubstituted alkyl group-containing alkoxy group, and a fluorine atom, a chlorine atom, a bromine atom. It may have an atom, a halogen atom such as an iodine atom, or an amino group represented by the following general formula as a substituent.

[0033]

Embedded image(Where R^Five, R⁶Is R^Three, R^FourOr the substitution defined by
Unsubstituted alkyl group, R ^Three, R^FourPermutation defined by
Represents an unsubstituted aryl group and R^FiveAnd R⁶But jointly
Or form a ring with the carbon atom on the aryl group
May be implemented. Examples of such a piperidino group,
Examples include a morpholino group and a eurololidyl group. )

In the general formulas (b) and (c), Ar ¹ ,
Ar ² and Ar ³ represent a substituted or unsubstituted arylene group. Specific examples include divalent groups derived from substituted or unsubstituted aryl groups represented by R ³ and R ⁴ .
The general formulas (b), (c), (d) and (e) have been described above, but the same symbols have the same definitions in other general formulas.

In the production of the aromatic polycarbonate resin of the present invention, diphenols having a triphenylamine structure represented by the above general formulas (b) and (c) are used, but the electric and mechanical properties are improved. For this purpose, any conventionally known diphenol can be used as it is as long as it is a diol having a charge transporting ability.

For example, distyrylbenzene derivatives (described in JP-A-9-71642), diphenethylbenzene derivatives (described in JP-A-9-104746), α-
Phenylstilbene derivatives (described in JP9702018), butadiene derivatives (described in JP-A-9-235367), hydrogenated butadiene derivatives (described in JP-A-9-87)
376), diphenylcyclohexane derivatives (described in JP-A-9-110976), distyryltriphenylamine derivatives (described in JP-A-9-268226).
Distyryldiamine derivatives (Japanese Patent Application No. 9
153846), diphenylstyrylbenzene derivatives (described in JP-A-9-221544 and 9-227669), stilbene derivatives (JP-A-9-15737).
8, JP9702582), m-phenylenediamine derivatives (Japanese Patent Application Laid-Open Nos.
No. 302085) and resorcinol derivatives (described in JP-A-9-328439).

The diphenols represented by the general formulas (b) and (c) used in the present invention are disclosed in JP-A-7-258399 and JP-A-8-269183, which were previously proposed by the present inventors.
, 9-151248, 9-241369 and 9-272735. Hereinafter, the general formula (a) will be described in detail.

In the general formula (a),

Embedded image (R ¹ and R ² are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, and Y is- COO- or the following formula

[0039]

Embedded image And Z represents a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group. )

Of these, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group each represent R
³ , a substituted or unsubstituted alkyl group defined for R ⁴ ,
The same applies to a substituted or unsubstituted aryl group. Further, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the case where Z is a substituted or unsubstituted arylene group include a divalent group derived from a substituted or unsubstituted aryl group defined for R 1.

Specific examples of the diol compound represented by the general formula (a) include 4-hydroxyphenyl-4-hydroxybenzoate, ethylene glycol-bis (4-hydroxybenzoate), and diethylene glycol-bis (4-
Hydroxybenzoate), triethylene glycol-
Examples include bis (4-hydroxybenzoate), 1,3-bis (4-hydroxyphenyl) tetramethyldisiloxane, and phenol-modified silicone oil.
Further, aromatic diol compounds containing an ester bond produced by reacting 2 mol of diol with 1 mol of isophthaloyl chloride or terephthaloyl chloride are also useful.

Further, known polycarbonate resin structural units can be used in combination. For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene ether glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-
Pentanediol, 1,6-hexanediol, 1,5
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 2-ethyl-1 , 3
-Propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 1,
4-cyclohexanediol, cyclohexane-1,4
Dimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, xylylene diol, 1,4-bis (2-hydroxyethyl) benzene, 1,4-bis (3-hydroxypropyl) benzene, 1,4 -Bis (4-hydroxybutyl) benzene, 1,4-bis (5
-Hydroxypentyl) benzene, 1,4-bis (6-
(Hydroxyhexyl) benzene, bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ) Ethane, 1,2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-
Phenylethane, 1,3-bis (4-hydroxyphenyl) -1,1-dimethylpropane, 2,2-bis (4-
(Hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 2,2-bis (4-hydroxy Phenyl) butane, 1,1- (4-hydroxyphenyl) -3
-Methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4- Bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) nonane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3-methyl-
4-hydroxyphenyl) propane, 2,2-bis (3
-Isopropyl-4-hydroxyphenyl) propane,
2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-) Hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-
Hydroxyphenyl) propane, 2,2-bis (3,5
-Dibromo-4-hydroxyphenyl) propane, 2,
2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl)
Cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,
5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane 1,1-bis (4-hydroxyphenyl) cycloheptane, 2,2-bis (4-hydroxyphenyl) norbornane, 2,2-bis (4-hydroxyphenyl) adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'
Tetramethyl-4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 3,3 '-Dimethyl-4,4'-dihydroxydiphenylsulfone,3,3'-diphenyl-4,
4'-dihydroxydiphenylsulfone, 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone,
Bis (4-hydroxyphenyl) ketone, bis (3-methyl-4-hydroxyphenyl) ketone, 3,3
3 ', 3'-tetramethyl-6,6'-dihydroxyspiro (bis) indane, 3,3', 4,4'-tetrahydro-4,4,4 ', 4'-tetramethyl-2,2' Spirobi (2H-1-benzopyran) -7,7 'diol, trans-2,3-bis (4-hydroxyphenyl) -2-butene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Bis (4-hydroxyphenyl) xanthene, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione, α, α, α ′, α ′
-Tetramethyl-α, α′-bis (4-hydroxyphenyl) -p-xylene, α, α, α ′, α′-tetramethyl-α, α′-bis (4-hydroxyphenyl) -m
-Xylene, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-
Dihydroxyphenoxathiin, 9,10-dimethyl-
2,7-dihydroxyphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxybenzothiophene, 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 2,7-dihydroxypyrene,
Hydroquinone, resorcin and the like can be mentioned.

Although the general formula (a) has been described above, the same symbols have the same definitions in other general formulas.

The content of the general formula (b) or (c) in the copolymerized polycarbonate resin of the structural unit represented by the general formula (a) and the structural unit represented by the general formula (b) or (c) Can be selected in any range,
Since the content of the structural unit represented by the general formula (b) or (c) corresponds to the charge transporting property of the polycarbonate resin, it is preferably 5 mol% or more, more preferably 20 mol% or more of all the structural units. It is desirable to contain.

The structure of the polycarbonate resin having a charge transporting property used in the electrophotographic photoreceptor of the present invention has been described above. The embodiment in which this is contained in the photosensitive layer will be described below.

FIGS. 1 to 6 are sectional views of the photosensitive member of the present invention. The photoreceptor of the present invention comprises one or more of the above-mentioned aromatic polycarbonate resins in the photosensitive layer 2 (2 ′,
2 ″, 2 ′ ″, 2 ″ ″, 2 ′ ″ ″), but depending on the manner of application, FIGS. 1, 2, 3,
It can be used as shown in FIG. 4, FIG. 5 or FIG.

The photoreceptor shown in FIG. 1 has a conductive support 1 on which a photosensitive layer 2 made of a sensitizing dye and an aromatic polycarbonate resin, and in some cases, a binder (binder resin) is provided. The aromatic polycarbonate resin here acts as a photoconductive substance, and the generation and movement of charge carriers required for light attenuation are performed through the aromatic polycarbonate resin. However, aromatic polycarbonate resins have almost no absorption in the visible region of light, and for the purpose of forming an image with visible light, sensitize by adding a sensitizing dye having absorption in the visible region. There is a need.

The photoreceptor shown in FIG. 2 is obtained by dispersing a charge generating substance 3 on a conductive support 1 in a charge transporting medium 4 comprising a charge transporting aromatic polycarbonate resin alone or in combination with a binder. A layer 2 'is provided. The aromatic polycarbonate resin here forms a charge transport medium alone or in combination with a binder, while the charge generating substance 3 (a charge generating substance such as an inorganic or organic pigment) generates a charge carrier. In this case, the charge transport medium 4 is mainly responsible for receiving the charge carriers generated by the charge generating substance 3 and transporting them. In this photoreceptor, the basic condition is that the charge generation substance and the aromatic polycarbonate resin do not overlap each other mainly in the visible region in the absorption wavelength region. This is because light must be transmitted to the surface of the charge generation material 3 in order to efficiently generate charge carriers in the charge generation material 3. Aromatic polycarbonate resin has a wavelength of 600n
m, it has almost no absorption, and in general, the visible region absorbs light in the near-infrared region and when combined with the charge generating material 3 that generates a charge carrier, it is particularly effective in functioning as a charge transport material. is there. The charge transport medium 4 may contain a low molecular charge transport material.

The photoreceptor shown in FIG. 3 comprises a conductive support 1 comprising a charge generation layer 5 mainly composed of a charge generation substance 3 and a charge transport layer 4 containing an aromatic polycarbonate resin having a charge transport ability. In this photoreceptor, light transmitted through the charge transport layer 4 reaches the charge generation layer 5 where charge carriers are generated. Reference numeral 4 denotes injection of charge carriers and transport of the charge carriers. Generation of charge carriers necessary for light attenuation is performed by the charge generation material 3, and transport of charge carriers is performed by the charge transport layer 4. Is the same as that described for the photoreceptor shown in Fig. 2. The charge transport layer 4 is formed by using the aromatic polycarbonate resin of the present invention alone or in combination with a binder. In the charge generation layer 5 The aromatic polycarbonate resin of the invention may be contained. May be used in combination a low-molecular-weight charge transport material in the photosensitive layer 2 'in the same purpose. The same applies to the photosensitive layers 2 ′ ″ to 2 ′ ″ ″ described later.

The photosensitive member shown in FIG. 4 has a protective layer 6 provided on the charge transport layer 4. In the case of this configuration, a protective layer is formed on the charge transport layer 4 in combination with the aromatic polycarbonate resin of the present invention or a binder. As a matter of course, formation on a low-molecular-weight dispersed charge transporting layer, which has been widely used, is effective. The photosensitive layer 2 'shown in FIG.
A protective layer may likewise be provided on the top.

The photosensitive member in FIG. 5 is the charge generating layer 5 in FIG.
Transport Layer 4 Containing Aromatic Polycarbonate Resin
And the mechanism of generation and transport of the charge carriers can be the same as described above. In this case, a protective layer 6 can be provided on the charge generation layer 5 as shown in FIG. 6 in consideration of mechanical strength.

In order to actually produce the photoreceptor of the present invention, if the photoreceptor shown in FIG. 1 is used, one or more aromatic polycarbonate resins having a charge transporting ability or a combination thereof with a binder is used. Then, a solution in which a sensitizing dye is added thereto is prepared, and the solution is coated on the conductive support 1 and dried to form the photosensitive layer 2.

The thickness of the photosensitive layer is 3 to 50 μm, preferably 5 to 40 μm. The amount of the aromatic polycarbonate resin in the photosensitive layer 2 is 30 to 100% by weight,
The amount of the sensitizing dye in the photosensitive layer 2 is 0.1 to 5% by weight, preferably 0.5 to 3% by weight.
The amount of the sensitizing dye is 0.1 to 5% by weight, preferably 0.5 to 3% by weight. Sensitizing infections include Brilliant Green, Victoria Blue B, Methyl Violet, Crystal Violet, Acid Violet 6
Triarylmethane dyes such as B, rhodamine B, rhodamine 6G, rhodamine G extra, eosin S,
Examples include xanthene dyes such as erythrosin, rose bengal and fluorescein, thiazine dyes such as methylene blue, and cyanine dyes such as cyanine.

In order to produce the photoreceptor shown in FIG.
One or two or more aromatic polycarbonate resins having a charge transporting ability or a binder are used in combination to disperse the fine particles of the charge generating substance 3 in a solution, which is coated on the conductive support 1 and dried. What is necessary is just to form the photosensitive layer 2 '.

The thickness of the photosensitive layer 2 'is 3 to 50 μm, preferably 5 to 40 μm. The amount of the aromatic polycarbonate resin having the charge transport ability in the photosensitive layer 2 'is 4
0 to 100% by weight, and the amount of the charge generating substance 3 in the photosensitive layer 2 'is 0.1 to 50% by weight, preferably 1 to 50% by weight.
20% by weight. Examples of the charge generating substance 3 include inorganic materials such as selenium, selenium-tellurium, cadmium sulfide, cadmium sulphide-selenium, and α-silicon, and examples of the organic material include CI Pigment Blue 25 (color index CI21180) and CI Pigment Red 41 ( CI2200), CIA Acid Red 5
2 (CI45100), sea eye basic red 3
(CI45210), azo pigments having a carbazole skeleton (described in JP-A-53-95033), azo pigments having a distyrylbenzene skeleton (JP-A-53-133)
445), an azo pigment having a triphenylamine skeleton (described in JP-A-53-132347), and an azo pigment having a dibenzothiophene skeleton (JP-A-54-2).
1728), an azo pigment having an oxadiazole skeleton (described in JP-A-54-12742),
Azo pigments having a fluorenone skeleton (JP-A-54-22)
834), azo pigments having a bisstilbene skeleton (described in JP-A-54-17733), azo pigments having a distyryloxadiazole skeleton (described in JP-A-54-2129), Azo pigments such as azo pigments having a distyrylcarbazole skeleton (described in JP-A-54-14967), for example, phthalocyanine pigments such as C.I. Pigment Blue 16 (CI74100), for example, C.I.
0), indigo-based pigments such as sea bat die (CI73030), Argo Scarlet B (manufactured by Bayer), Indance Scarlet R (manufactured by Bayer)
And the like. These charge generating substances may be used alone or in combination of two or more.

In addition, among the above-described charge generating substances, a photosensitive member having high sensitivity and high durability can be obtained by combining with the phthalocyanine pigment. The phthalocyanine pigment is a compound having a phthalocyanine skeleton represented by the following formula, and M (center metal) includes a metal and a metal-free (hydrogen) element.

[0057]

Embedded image

M (center metal) mentioned here is H,
Li, Be, Na, Mg, Al, Si, K, Ca, S
c, Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ge, Y, Zr, Nb, Mo, Tc, R
u, Rh, Pd, Ag, Cd, In, Sn, Sb, B
a, Hf, Ta, W, Re, Os, Ir, Pt, Au,
Hg, Tl, La, Ce, Pr, Nd, Pm, Sm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
It is composed of a simple substance such as u, Th, Pa, U, Np, and Am, or two or more elements such as an oxide, a chloride, a fluoride, a hydroxide, and a bromide. The central metal is not limited to these elements. The charge generating substance having a phthalocyanine skeleton in the present invention is at least a compound represented by the general formula (N)
It is only necessary to have a basic skeleton as described above, and may have a multimeric structure such as a dimer or trimer, or may have a higher molecular structure. Further, those having various substituents in the basic skeleton may be used.

Of these various phthalocyanines, oxotitanium phthalocyanine having TiO as the central metal and non-metal phthalocyanine having H are particularly preferable in terms of photoreceptor characteristics.

It is also known that these phthalocyanines have various crystal systems. For example, oxotitanium phthalocyanine has α, β, γ, m, and y types, and copper phthalocyanine has α, β, It has a polymorphism such as γ. Even with phthalocyanines having the same central metal, various characteristics change as the crystal system changes. Among them, it has been reported that the photoreceptor characteristics also change with such a change in the crystal system. (Journal of the Society of Electrophotography, Vol. 29, No. 4, 1990)
Each phthalocyanine has an optimal crystal system in terms of the photoreceptor characteristics. Particularly, in the case of oxotitanium phthalocyanine, a y-type crystal system is desirable.

Further, these charge generating substances may be a mixture of two or more kinds of charge generating substances having a phthalocyanine skeleton. Further, it may be mixed with other charge generating substances.

Further, to produce the photoreceptor shown in FIG.
The charge generating substance is vacuum-deposited on the conductive support 1, or a dispersion liquid in which the fine particles 3 of the charge generating substance are dispersed in an appropriate solvent in which a binder is dissolved if necessary is applied and dried. If so, the surface is finished by a method such as buffing, the film thickness is adjusted, and the like, to form the charge generation layer 5, on which one or more aromatic polycarbonate resins or binders having charge transport ability are formed. The dissolved and used solution may be applied and dried to form the charge transport layer 4. Here, the charge generation material used for forming the charge generation layer 5 is the same as that described for the photosensitive layer 2 '.

The thickness of the charge generation layer 5 is 5 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer 4 is 3 to 50 μm.
μm, preferably 5 to 40 μm is suitable. In the case where the charge generating layer 5 is of a type in which the fine particles 3 of the charge generating layer material are dispersed in a binder, the ratio of the fine particles 3 of the charge generating material to the charge generating layer 5 is preferably 10 to 100% by weight. Is about 50 to 100% by weight. Further, the amount of the polycarbonate resin having the charge transport ability in the charge transport layer 4 is 40 to 100% by weight.

As described above, the photosensitive layer 2 ″ in FIG. 3 may contain a low-molecular charge transport material. Examples of the charge transport material used herein include the following.

Oxazole derivatives and oxadiazole derivatives (JP-A-52-139065 and JP-A-52-13905)
No. 66), imidazole derivatives, triphenylamine derivatives (described in JP-A-3-285960), benzidine derivatives (described in JP-B-58-32372), α-phenylstilbene derivatives (described in JP-A-5-28572).
7-73075), hydrazone derivatives (Japanese Unexamined Patent Publication Nos. 55-15495 and 55-156954),
JP-A-55-52063 and JP-A-56-81850), triphenylmethane derivatives (JP-B-51-52063).
No. 10983), anthracene derivatives (described in JP-A-51-94829), styryl derivatives (described in JP-A-56-29245 and JP-A-58-198043), carbazole derivatives (described in JP-A-59-198043). 58-5
8552), pyrene derivatives (Japanese Unexamined Patent Application Publication No.
No. 4812).

In order to produce the photosensitive member shown in FIG.
The protective layer 6 is provided by dissolving and coating the aromatic polycarbonate resin having the charge transporting ability of the present invention alone or in combination with a binder on the photoreceptor shown in FIG. The thickness of the protective layer is preferably from 0.15 to 10 μm. Protective layer 6
The amount of the aromatic polycarbonate resin of the present invention occupying therein is 40 to 100% by weight.

To prepare the photoreceptor shown in FIG. 5, a solution in which an aromatic polycarbonate resin having a charge transporting property or a binder is dissolved and used in combination with a binder is applied to the conductive support 1.
After drying to form the charge transport layer 4, a dispersion in which fine particles of a charge generation layer material are dispersed in a solvent in which a binder is dissolved as required is coated on the charge transport layer by a method such as spray coating and dried. Then, the charge generation layer 5 may be formed. The amount ratio of the charge generation layer or the charge transport layer is the same as that described in FIG.

By forming the above-described protective layer 6 on the charge generating layer 5 of the photosensitive member thus obtained,
Can be prepared.

In the production of any of these photoconductors, the conductive support 1 may be made of a metal plate or a metal foil such as aluminum, a plastic film on which a metal such as aluminum is deposited, or a paper which has been subjected to a conductive treatment. Used.

As the binder, condensed resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone and polycarbonate, and vinyl polymers such as polyvinylketone, polystyrene, poly-N-vinylcarbazole and polyacrylamide are used. But
All insulating and adhesive resins can be used. If necessary, a plasticizer is added to the binder. Examples of such a plasticizer include halogenated paraffin, dimethylnaphthalene, and dibutylphthalate. If necessary, additives such as an antioxidant, a light stabilizer, a heat stabilizer and a lubricant can be added.

Further, the photosensitive member obtained as described above may be provided with an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary. Materials used for these layers include polyamide, nitrocellulose, aluminum oxide, and titanium oxide.
m or less is preferable.

To make a copy using the photoreceptor of the present invention,
After the photosensitive surface is charged and exposed, development is performed and, if necessary, transfer to paper or the like. The photoconductor of the present invention has high sensitivity,
In particular, it has excellent durability.

[0073]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to examples.

Production Example 1 A 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel was charged with N- {4- [2,2-bis (4-
(Hydroxyphenyl) vinyl] phenyl} -N, N-bis (4-tolyl) amine 2.69 g (5.56 mmol), ethylene glycol bis (4-hydroxybenzoate) 1.99 g (6.58 mmol), dehydrated pyridine 20 ml and 20 ml of dehydrated dichloromethane.
The mixture was stirred and dissolved under a nitrogen gas stream. 2 internal temperature in a water bath
At 0 ° C., 1.44 g of bis (trichloromethane) carbonate, a trimer of phosgene, was vigorously stirred.
(4.85 mmol) in 10 ml of dehydrated dichloromethane was added dropwise over 20 minutes, and the mixture was reacted at room temperature for 1.5 hours. After stopping the stirring, the reaction solution was washed with a 5% aqueous hydrochloric acid solution and then with ion-exchanged water. The resulting solution was dropped into 1.5 liters of methanol to precipitate a yellow polycarbonate resin, which was then dried.
1) was obtained. The suffix of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all the structural units is 1. The results of the elemental analysis are shown in Table 1.
This corresponds to the value calculated as a random copolymer polycarbonate resin composed of two constituent units having the respective composition ratios of 1. The molecular weight of this product was measured by gel permeation chromatography, and the molecular weight in terms of polystyrene and the glass transition temperature determined by differential scanning calorimetry are shown in Table 1.

Production Example 2 A 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel was charged with N- {4- [2,2-bis (4-
(Hydroxyphenyl) vinyl] phenyl} -N, N-bis (4-tolyl) amine 3.23 g (6.67 mmol), diethylene glycol bis (4-hydroxybenzoate) 2.42 g (6.98 mmol), 25 ml of dehydrated pyridine Then, 25 ml of dehydrated dichloromethane was added and dissolved by stirring under a nitrogen gas stream. While maintaining the internal temperature at 20 ° C. in a water bath, bis (trichloromethane) carbonate 1.62, which is a trimer of phosgene, was stirred vigorously.
g (5.46 mmol) in 10 ml of dehydrated dichloromethane
Was added dropwise over 20 minutes, and the mixture was reacted at room temperature for 1 hour. After stopping the stirring, the reaction solution was washed with a 5% aqueous hydrochloric acid solution and then with ion-exchanged water. The resulting solution was dropped into 1.5 liters of methanol to precipitate a yellow polycarbonate resin, which was dried, and then a random copolymer polycarbonate resin (resin No. 2) shown in Table 1
I got The suffix of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all the structural units is 1. The results of the elemental analysis are shown in Table 1. This is consistent with the value calculated as a random copolymer polycarbonate resin composed of two constituent units having the respective composition ratios of 2. The molecular weight of this product was measured by gel permeation chromatography, and the molecular weight in terms of polystyrene and the glass transition temperature determined by differential scanning calorimetry are shown in Table 1.

Production Example 3 A 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel was charged with N- {4- [2,2-bis (4-
[Hydroxyphenyl) vinyl] phenyl} -N, N-bis (4-tolyl) amine 2.69 g (5.56 mmol), 4-hydroxyphenyl-4-hydroxybenzoate 1.95 g (8.47 mmol), dehydrated pyridine 20 ml and 20 ml of dehydrated dichloromethane were added and dissolved by stirring under a nitrogen gas stream. 20 internal temperature in a water bath
1.66 g of bis (trichloromethane) carbonate, a trimer of phosgene, maintained at ℃ and with vigorous stirring.
A solution of (5.59 mmol) in 10 ml of dehydrated dichloromethane was added dropwise over 20 minutes, and the mixture was reacted at room temperature for 1 hour. After stopping the stirring, the reaction solution was washed with a 5% aqueous hydrochloric acid solution and then with ion-exchanged water. The resulting solution was dropped into 1.5 liters of methanol to precipitate a yellow polycarbonate resin and dried to obtain a random copolymerized polycarbonate resin (Resin No. 3) shown in Table 1. The suffix of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all the structural units is 1. The results of the elemental analysis are shown in Table 1. 3 corresponds to a value calculated as a random copolymer polycarbonate resin composed of two constituent units having respective composition ratios of 3. The molecular weight of this product was measured by gel permeation chromatography, and the molecular weight in terms of polystyrene and the glass transition temperature determined by differential scanning calorimetry are shown in Table 1.
It was shown to.

Production Example 4 A 200 ml four-necked flask equipped with a stirrer, a thermometer, a silica gel tube and a dropping funnel was charged with 1,1-bis (4-hydroxyphenyl) -1- [1-diphenol as a diphenol having charge transport ability. 4- (di-p-tolylaminophenyl)] ethane 3.22 (6.6 mmol), 2.34 g of 4-hydroxyphenyl-4-hydroxybenzoate
(10.2 mmol), 18 ml of dehydrated pyridine and 25 ml of dehydrated dichloromethane were added and dissolved by stirring under a stream of nitrogen gas. 1.90 g (6.40 mmol) of bis (trichloromethane) carbonate, a trimer of phosgene, is maintained while maintaining the internal temperature at 20 ° C. in a water bath and stirring vigorously.
Was dissolved in 10 ml of dehydrated dichloromethane and added dropwise over 20 minutes. After the addition, the mixture was reacted at room temperature for 1 hour. After stopping the stirring, the reaction solution was washed with a 5% aqueous hydrochloric acid solution and then with ion-exchanged water. The resulting solution was dropped into 1.5 liters of methanol to precipitate a white polycarbonate resin and dried to obtain a random copolymerized polycarbonate resin (Resin No. 4) shown in Table 1. The suffix of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all the structural units is 1. The results of the elemental analysis are shown in Table 1. 4 corresponds to the value calculated as a random copolymer polycarbonate resin composed of two constituent units having the respective composition ratios. The molecular weight of this product was measured by gel permeation chromatography. The molecular weight in terms of polystyrene and the glass transition temperature determined by differential scanning calorimetry are shown in Table 1.

Production Example 5 A 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel was charged with N- {4- [2,2-bis (4-
(Hydroxyphenyl) vinyl] phenyl} -N, N-bis (4-tolyl) amine 2.69 g (5.56 mmol), 1,6-bis (4-hydroxybenzoyloxy) -1H, 1H, 6H, 6H- 2.06 g (4.10 mmol) of perfluorohexane, 25 m of dehydrated pyridine
l and 15 ml of dehydrated dichloromethane were added and dissolved by stirring under a stream of nitrogen gas. While maintaining the internal temperature at 20 ° C. in a water bath, 1.34 g (4.5 g) of bis (trichloromethane) carbonate, a trimer of phosgene, was vigorously stirred.
(2 mmol) in 10 ml of dehydrated dichloromethane was added dropwise over 20 minutes, and the mixture was allowed to react at room temperature for 1 hour. After the stirring was stopped, the reaction solution was washed with a 5% hydrochloric acid aqueous solution,
And it washed with ion exchange water. The resulting solution is 1.5
A yellow polycarbonate resin was precipitated by dropping in 1 liter of methanol and dried to obtain a random copolymer polycarbonate resin (resin No. 5) shown in Table 1. The suffix of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all the structural units is 1. The results of the elemental analysis are shown in Table 1. 5 corresponds to the value calculated as a random copolymer polycarbonate resin composed of two constituent units having the respective composition ratios.
The molecular weight of this product was measured by gel permeation chromatography, and the molecular weight in terms of polystyrene and the glass transition temperature determined by differential scanning calorimetry are shown in Table 1.

Production Example 6 A 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel was charged with N- {4- [2,2-bis (4-
(Hydroxyphenyl) vinyl] phenyl} -N, N-bis (4-tolyl) amine 3.23 g (6.67 mmol), 1,4-bis (4-hydroxybenzoyloxy) -1H, 1H, 4H, 4H- 2.44 g (6.07 mmol) of perfluorobutane, 30 m of dehydrated pyridine
and 20 ml of dehydrated dichloromethane were added and dissolved by stirring under a stream of nitrogen gas. While maintaining the internal temperature at 20 ° C. in a water bath, 1.76 g (5.9 g) of bis (trichloromethane) carbonate, a trimer of phosgene, was vigorously stirred.
(3 mmol) in 10 ml of dehydrated dichloromethane was added dropwise over 20 minutes, and the mixture was allowed to react at room temperature for 1 hour. After the stirring was stopped, the reaction solution was washed with a 5% hydrochloric acid aqueous solution,
And it washed with ion exchange water. The resulting solution is 1.5
A yellow polycarbonate resin was precipitated by dropping into 1 liter of methanol and dried to obtain a random copolymer polycarbonate resin (resin No. 6) shown in Table 1. The suffix of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all the structural units is 1. The results of the elemental analysis are shown in Table 1. 6 corresponds to the value calculated as a random copolymer polycarbonate resin composed of two constituent units having the respective composition ratios.
The molecular weight of this product was measured by gel permeation chromatography, and the molecular weight in terms of polystyrene and the glass transition temperature determined by differential scanning calorimetry are shown in Table 1.

Production Example 7 A 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel was charged with 1,1-bis (4-hydroxyphenyl) -1- [1-diphenol as a diphenol having charge transport ability. 4- (di-p-tolylaminophenyl)] ethane 3.23 g (6.64 mmol), p-phenylene-bis (4-hydroxybenzoate) 2.4
2 g (6.91 mmol), 30 ml of dehydrated pyridine and 30 ml of dehydrated dichloromethane were added and dissolved by stirring under a stream of nitrogen gas. Keep the internal temperature at 20 ° C in a water bath,
A solution prepared by dissolving 1.61 g (5.43 mmol) of bis (trichloromethane) carbonate, a trimer of phosgene, in 10 ml of dehydrated dichloromethane was stirred vigorously.
The mixture was added dropwise at 0 minutes, and the mixture was reacted at room temperature for 2 hours. After stopping the stirring, the reaction solution was washed with a 5% aqueous hydrochloric acid solution and then with ion-exchanged water. The resulting solution was dropped into 1.5 liters of methanol to precipitate a white polycarbonate resin and dried to obtain a random copolymer polycarbonate resin (Resin No. 7) shown in Table 1. The suffix of the structural unit in the structural formula represents the composition ratio of each structural unit when the number of all the structural units is 1. Table 1 shows the results of elemental analysis.
Is shown along with the resin No. 7 corresponds to the value calculated as a random copolymer polycarbonate resin composed of two constituent units having the respective composition ratios. Table 1 shows the glass transition temperature obtained from the differential scanning calorimetry.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

[Table 4]

[0085]

[Table 5]

Example 1 A solution of a polyamide resin (CM-80000: manufactured by Toray Industries, Ltd.) dissolved in a mixed solvent of methanol and butanol was applied on an aluminum plate with a doctor blade, air-dried, and dried to a thickness of 0.3 μm.
Was provided. On this, a bisazo compound represented by the following formula as a charge generating material is pulverized by a ball mill in a mixed solvent of cyclohexanone and 2-butanone, and the obtained dispersion is applied with a doctor blade, and naturally dried,
A 0.5 μm charge generation layer was formed.

[0087]

Embedded image

Next, as the charge transporting material, the resin No. obtained in Production Example 1 was used. 1 polycarbonate resin was dissolved in dichloromethane, and this solution was applied on the charge generation layer with a doctor blade, air-dried, and then dried at 120 ° C. for 20 minutes.
After drying for 20 minutes, a charge transporting layer having a thickness of 20 μm was formed. 1 was produced.

Examples 2 to 6 Resin No. used in Example 1 In the same manner as in Example 1 except that the polycarbonate resin of the present invention shown in Table 1 was used instead of Photoreceptor No. 1, 2-No. 6 were each produced.

The photosensitive member No. 1 to N
o. 6 commercially available electrostatic copying paper test equipment [Kawaguchi Corporation
-6kV in a dark place using SP428 manufactured by Denki Seisakusho
After charging for 20 seconds by corona discharge, the surface of photoreceptor
Measure the surface potential Vm (V) and leave it in a dark place for another 20 seconds.
After that, the surface potential V₀(V) was measured. Then tongue
Illumination on the photoreceptor surface is reduced to 5.3lux
Irradiate so that V ₀Time until becomes 1/2
(Seconds), and the exposure amount E_1/2Calculate (lux · sec)
did. Table 2 shows the results.

Further, after charging the above photoreceptor using a commercially available electrophotographic copying machine, it is irradiated with light through the original drawing to form an electrostatic latent image, and developed using a dry developer.
The obtained image (toner image) is electrostatically transferred onto plain paper,
Upon fixing, a clear transferred image was obtained. Similarly, when a wet type developer was used as the developer, a clear transfer image was obtained.

[0092]

[Table 6]

[0093]

The electrophotographic photoreceptor of the present invention contains, as an active ingredient, a polycarbonate resin containing at least a specific structural unit in a photosensitive layer. These polycarbonate resins have a high charge transporting ability and Since the electrophotographic photoreceptor of the present invention can have high mechanical strength, it has high sensitivity and high durability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a layer configuration of an electrophotographic photosensitive member according to the present invention.

FIG. 2 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photoreceptor according to the present invention.

FIG. 3 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present invention.

FIG. 4 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present invention.

FIG. 5 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present invention.

FIG. 6 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2, 2 ', 2 ", 2"', 2 "", 2 "" 'Photosensitive layer 3 Charge generating substance 4 Charge transport layer or charge transport medium 5 Charge generating layer 6 Protection layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaomi Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Kazuki Nagai 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd. (72) Inventor Shinichi Kawamura 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company Company, Ltd. (72) Susumu Suzuka 66-2 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Hodogaya Chemical Industry (72) Inventor Katsuhiro Morooka 66-2 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa F-term (reference) 2H068 AA13 AA20 BB20 BB26 BB27 BB49 BB52 BB53 EA04 4J029 AA10 AB07 AC02 AD01 AE04 BE07 BH01 DA02 HA01 HC01 HC02 HC09 JC231 KE09

Claims (6)

[Claims] 1. A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin obtained by solution polymerization of a diphenol compound having a triarylamine structure and a diol compound represented by the following general formula (a): A photoconductor for electrophotography, comprising: Embedded image (Wherein R ¹ and R ² are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, Y is -COO- or the following formula: And Z represents a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group. ) 2. A photosensitive layer containing an aromatic polycarbonate resin, wherein the diphenol compound having a triarylamine structure according to claim 1 is a diphenol compound represented by the following general formula (b), as an active ingredient: A photoconductor for electrophotography, characterized by: Embedded image (In the formula, Ar ¹ , Ar ² , and Ar ³ represent a substituted or unsubstituted arylene group. R ³ and R ⁴ are the same or different acyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups. Represents.) 3. A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin in which the diphenol compound having a triarylamine structure according to claim 1 is a diphenol compound represented by the following general formula (c): A photoconductor for electrophotography, characterized by: Embedded image (In the formula, Ar ¹ , Ar ² , Ar ³ , R ³ , and R ⁴ are the same as defined above.) 4. A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin represented by the following general formula (d) obtained by subjecting the above general formulas (a) and (b) to solution polymerization. An electrophotographic photoreceptor characterized by being provided. Embedded image (Wherein, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ , R ⁴ ,
a and b are the same as defined above. k is an integer of 5 to 5000, j is an integer of 5 to 5000, and 0 <k / (k +
j) ≦ 1) 5. A photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin represented by the following general formula (e) obtained by solution polymerization of the above general formulas (a) and (c). An electrophotographic photoreceptor characterized by being provided. Embedded image (Wherein, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ , R ⁴ ,
a and b are the same as defined above. k is an integer of 5 to 5000, j is an integer of 5 to 5000, and 0 <k / (k +
j) ≦ 1) 6. The solution polymerization according to claim 1, wherein dehydrated pyridine is used as a deoxidizing agent, and its ratio in a reaction solvent is 5 to 1%.
A photoconductor for electrophotography, comprising a photosensitive layer containing an aromatic polycarbonate resin produced at 00% by volume as an active ingredient.