JP3155828B2 - Polycarbonate copolymer, method for producing the same, and electrophotographic photoreceptor using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbonate copolymer, a method for producing the same, and an electrophotographic photosensitive member using the same. More specifically, the present invention relates to a novel polycarbonate copolymer which can be suitably used as a binder resin in a photosensitive layer of an electrophotographic photosensitive member, a material for an EL device, and the like, a method for producing the same, and the polycarbonate copolymer The present invention relates to an electrophotographic photoreceptor produced using the same and having excellent printing durability and electrophotographic characteristics.

[0002]

2. Description of the Related Art Polycarbonate is used as a material in various fields, but with the expansion of application fields, development of a material having even better performance is desired.

In a recent electrophotographic photoreceptor, a laminated electrophotographic photoreceptor, that is, a photosensitive layer includes a charge generation layer (CGL) for generating a charge upon exposure and a charge transport layer (CTL) for transporting a charge. And a single-layer type electrophotographic photoreceptor (OPC) having at least two layers of: a photosensitive layer comprising a single layer in which a charge generating substance and a charge transporting substance are dispersed in a binder resin. Has been used. As the binder resin of the charge transport layer of the laminated electrophotographic photosensitive member and the photosensitive layer of the single-layer electrophotographic photosensitive member,
Polycarbonate resins made from bisphenol A or bisphenol Z are widely used. Polycarbonate resin using bisphenol A or bisphenol Z as a raw material has good compatibility with a charge transporting material. Therefore, when a photoconductor is produced by using this as a binder resin in a photosensitive layer, electric characteristics are good, and A photoreceptor having relatively high mechanical strength can be obtained.

However, when the charge transport layer is formed using a polycarbonate resin made of bisphenol A or bisphenol Z as a binder resin, the following problems have been found. In producing the photoreceptor, when applying the photosensitive layer, the coating liquid may be whitened (gelled) or the photosensitive layer may be easily crystallized depending on the solvent used. In the portion where the crystallization has occurred, there is no light attenuation, the charge or the residual potential remains, and the defect appears in image quality. The charge transport layer or photosensitive layer using a polycarbonate resin made of bisphenol A or bisphenol Z as a binder resin has poor adhesion to a base and is easily peeled off, or is damaged due to insufficient surface hardness, or the surface is worn. There is a disadvantage that the printing life is shortened. In general, the term “underlayer” as used herein refers to a conductive substrate in the case of a single-layer type photosensitive member and a reverse-layer type photosensitive member, and a charge transport layer and a charge generation layer on the conductive member like a positively charged electrophotographic photosensitive member. When layers are sequentially laminated, a conductor serves as a base, and a blocking layer or an intermediate layer is provided between the conductor and the charge transport layer or between the charge generation layer and the charge transport layer for the purpose of improving electrophotographic characteristics. If they do, they become the groundwork.

[0005]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. An object of the present invention is to solve the above-mentioned problems observed in a conventional electrophotographic photosensitive member using a polycarbonate resin made of bisphenol A or bisphenol Z as a binder resin for a photosensitive layer, and to prepare an electrophotographic photosensitive member. Coating liquid is whitened (gelled)
It is an object of the present invention to provide a novel polycarbonate copolymer which does not lose its properties and has excellent mechanical strength over a long period of time.

Another object of the present invention is to provide a suitable method for producing the above polycarbonate copolymer.

Further, the present invention is produced by using the above polycarbonate copolymer as a binder resin, maintains excellent mechanical strength for a long period of time, particularly has high surface hardness, excellent printing durability, and excellent It is an object of the present invention to provide an electrophotographic photoreceptor that maintains the electrophotographic characteristics.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, a specific bisphenol-based polycarbonate having a pyrazine structure in a repeating unit was used as a binder resin for an electrophotographic photosensitive member. It has been found that an electrophotographic photoreceptor manufactured using the same is excellent in printing durability and has good electrophotographic properties, and based on this finding, the present invention was completed. Was.

That is, the present invention provides a compound represented by the following general formula (I):

[0010]

Embedded image [Wherein, R ¹ and R ² are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. There, a and b are each independently an integer of 0 to 4, X is a single bond, -O -, - S -, - SO -, - SO 2
—, —CR ³ R ⁴ — (where R ³ and R ⁴ are each independently
It is a hydrogen atom, a trifluoromethyl group, a C1-C6 alkyl group, or a C6-C12 substituted or unsubstituted aryl group. ), A 1,1-cycloalkylene group having 5 to 11 carbon atoms or an α, ω-alkylene group having 2 to 10 carbon atoms. And a repeating unit (I) represented by the following general formula (II):

[0011]

Embedded image Wherein R ⁵ is a halogen atom, an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ⁶ is an alkyl group having 1 to 30 carbon atoms, A halogenated alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 1 to 30 carbon atoms, an alkenyl group or alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom, Is 0
Is an integer of 4, and d is an integer of 0 to 2, provided that both c and d are not 0. And the content of the repeating unit (II) is 0.01 in a molar ratio of the repeating unit (II) to the total of the repeating unit (I) and the repeating unit (II). ~
0.9, and 0.5 g / d using methylene chloride as a solvent.
An object of the present invention is to provide a polycarbonate copolymer having a reduced viscosity [η _sp / c] at 20 ° C. of a 1-concentration solution of 0.3 dl / g or more.

The polycarbonate copolymer of the present invention may be a copolymer comprising one kind of the repeating unit (I) and one kind of the repeating unit (II), and may contain two or more kinds of the repeating unit (I). And may contain two or more kinds of repeating units (II).

In the polycarbonate copolymer of the present invention, the molar ratio of the repeating unit (II) to the total of the repeating unit (I) and the repeating unit (II), (II) / [(I ) + (II)], 0.01
To 0.9, preferably 0.1 to 0.4. When the molar ratio of the repeating unit (II) is less than 0.01, when used as a binder resin in an electrophotographic photosensitive member, the printing durability and electrophotographic properties are insufficiently improved. On the other hand, if the molar ratio exceeds 0.9, a part of the polycarbonate copolymer is crystallized during the production of the electrophotographic photosensitive member, and it is impossible to produce a photosensitive member having sufficient printing durability and electrophotographic characteristics. Become.

Incidentally, the polycarbonate copolymer of the present invention may have other repeating units other than those described above as long as the object of the present invention is not hindered.

The polycarbonate copolymer of the present invention is prepared by adding a 0.5 g / dl solution of methylene chloride as a solvent.
The reduced viscosity [η _sp / c] at 0 ° C. is 0.3 dl / g or more, preferably in the range of 0.3 to 2.0 dl / g.
When the reduced viscosity [η _sp / c] is less than 0.3 dl / g, the mechanical strength of the polycarbonate copolymer is low, and particularly, the surface hardness of the layer containing the polycarbonate copolymer is insufficient,
The photoreceptor wears, shortening the printing life. Reduced viscosity [η _sp
/ c] exceeds 2.0 dl / g, the solution viscosity of the polycarbonate copolymer increases, and it may be difficult to produce a photoconductor by a solution coating method.

The present invention also provides a method for producing the above polycarbonate copolymer of the present invention. The method for producing the polycarbonate copolymer of the present invention is not particularly limited. However, according to the method of the present invention, the above polycarbonate copolymer can be suitably produced.

That is, the method for producing the polycarbonate copolymer of the present invention is represented by the following general formula (III):

[0018]

Embedded image Wherein R ¹ , R ² , a and b have the same meaning as described above. A dihydric phenol (III) represented by the following general formula (IV)

[0019]

Embedded image Wherein R ⁵ , R ⁶ , c and d have the same meaning as described above. And a pyrazine compound (IV) represented by the formula (I):

This reaction is carried out using various carbonyl halides such as phosgene as a carbonate-forming compound, haloformates such as a chloroformate compound or a carbonate compound in the presence of a suitable acid binder. It is carried out by a method such as performing a polycondensation reaction, or performing a transesterification reaction using bisaryl carbonates as the carbonate-forming compound.

Examples of the dihydric phenol (III) represented by the general formula (III) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, , 2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 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, 4,4′-dihydroxytetraphenylmethane, 1,1-bis (4-hydroxy Phenyl)-
1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl)
Sulfide, bis (4-hydroxyphenyl) sulfone, 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) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfone, 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-te
rt-butyl-4-hydroxy-5-methylphenyl)
-1-phenylmethane, 1,1-bis (2-tert-
Amyl-4-hydroxy-5-methylphenyl) 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, 2,2-bis (3,5-dichloro-4-
Hydroxyphenyl) propane, 2,2-bis (3,5
-Dibromo-4-hydroxyphenyl) propane, 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, bis (3-fluoro-4-hydroxyphenyl) ether, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane,
4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4 '
-Dihydroxy-3,3'-dicyclohexylbiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-phenyl −
4-hydroxyphenyl) propane, 1,1-bis (3
-Phenyl-4-hydroxyphenyl) cyclohexane, bis (3-phenyl-4-hydroxyphenyl) sulfone, 4,4'-dihydroxybenzophenone and the like. These dihydroxyaryl compounds can be used alone or in a combination of two or more.

Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxytetraphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4 -Hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-
4-hydroxyphenyl) propane, 4,4'-dihydroxybiphenyl and 2,2-bis (3-phenyl-4
-Hydroxyphenyl) propane is used.

As the pyrazine compound (IV), specifically, 2,5-bis (4-hydroxyphenyl) -3
-Methylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-ethylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-propylpyrazine, 2,5-bis (4-hydroxyphenyl)- 3-isopropylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-
Butylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-isobutylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-sec-butylpyrazine,
2,5-bis (4-hydroxyphenyl) -3-ter
t-butylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-pentylpyrazine, 2,5-bis (4-
(Hydroxyphenyl) -3-isopentylpyrazine,
2,5-bis (4-hydroxyphenyl) -3-neopentylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-tert-pentylpyrazine, 2,5-bis (4-hydroxyphenyl) -3 Hexylpyrazine,
2,5-bis (4-hydroxyphenyl) -3-isohexylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-heptylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-octyl Pyrazine, 2,5-bis (4-hydroxyphenyl) -3-nonylpyrazine,
2,5-bis (4-hydroxyphenyl) -3-decylpyrazine, 2,5-bis (4-hydroxyphenyl)-
3-undecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-dodecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-tridecylpyrazine, 2,5-bis (4-hydroxy Phenyl) -3-tetradecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-pentadecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-hexadecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-heptadecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-octadecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-nonadecylpyrazine, 2, 5-bis (4-hydroxyphenyl) -3-icosylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-phenylpyrazine 2,5-bis (4-hydroxyphenyl) -3-benzyl pyrazine, 2,5-bis (4-hydroxyphenyl) -3- Nafutopirajin,
2,5-bis (4-hydroxyphenyl) -3- (fluoromethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3- (difluoromethyl) pyrazine,
5-bis (4-hydroxyphenyl) -3- (trifluoromethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3- (chloromethyl) pyrazine, 2,5-
Bis (4-hydroxyphenyl) -3- (dichloromethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3- (trichloromethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3- (Bromomethyl)
Pyrazine, 2,5-bis (4-hydroxyphenyl)-
3- (dibromomethyl) pyrazine, 2,5-bis (4-
(Hydroxyphenyl) -3- (tribromomethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3-
Fluoropyrazine, 2,5-bis (4-hydroxyphenyl) -3-chloropyrazine, 2,5-bis (4-hydroxyphenyl) -3-bromopyrazine, 2,5-bis (4-hydroxyphenyl) -3 -Iodopyrazine,
2,5-bis (3,5-dimethyl-4-hydroxyphenyl) -3-methylpyrazine, 2,5-bis (3,5-
Dimethyl-4-hydroxyphenyl) -3-ethylpyrazine, 2,5-bis (3,5-dimethyl-4-hydroxyphenyl) -3-propylpyrazine, 2,5-bis (3,5-diphenyl-4- Hydroxyphenyl) -3
-Methylpyrazine, 2,5-bis (3,5-diphenyl-4-hydroxyphenyl) -3-ethylpyrazine,
2,5-bis (3,5-diphenyl-4-hydroxyphenyl) -3-propylpyrazine, 2,5-bis (3
5-dichloro-4-hydroxyphenyl) -3-methylpyrazine, 2,5-bis (3,5-dichloro-4-hydroxyphenyl) -3-ethylpyrazine, 2,5-bis (3,5-dichloro- 4-hydroxyphenyl) -3-
Propylpyrazine, 2,5-bis (3,5-dibromo-
4-hydroxyphenyl) -3-methylpyrazine, 2,
5-bis (3,5-dibromo-4-hydroxyphenyl) -3-ethylpyrazine, 2,5-bis (3,5-dibromo-4-hydroxyphenyl) -3-propylpyrazine, 2,5-bis ( 4-hydroxyphenyl) -3,
6-dimethylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-diethylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dipropylpyrazine, 2,5-bis ( 4-hydroxyphenyl) -3,
6-diisopropylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dibutylpyrazine, 2,5
-Bis (4-hydroxyphenyl) -3,6-diisobutylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-di-sec-butylpyrazine, 2,5-
Bis (4-hydroxyphenyl) -3,6-di-ter
t-butylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dipentylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-diisopentylpyrazine, 2,5-bis (4-hydroxyphenyl)-
3,6-dineopentylpyrazine, 2,5-bis (4-
(Hydroxyphenyl) -3,6-di-tert-pentylpyrazine, 2,5-bis (4-hydroxyphenyl)
-3,6-dihexylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-diisohexylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6
-Diheptylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dioctylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dinonylpyrazine, 2,5-bis (4- Hydroxyphenyl) -3,
6-didecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-diundecylpyrazine, 2,5-
Bis (4-hydroxyphenyl) -3,6-didodecylpyrazine, 2,5-bis (4-hydroxyphenyl)-
3,6-ditridecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-ditetradecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6
-Dipentadecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dihexadecylpyrazine,
2,5-bis (4-hydroxyphenyl) -3,6-diheptadecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dioctadecylpyrazine, 2,5
-Bis (4-hydroxyphenyl) -3,6-dinonadecylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-diicosylpyrazine, 2,5-bis (4
-Hydroxyphenyl) -3,6-divinylpyrazine,
2,5-bis (4-hydroxyphenyl) -3,6-diallylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dipropenylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-diisopropenylpyrazine, 2,5-bis (4-hydroxyphenyl)
-3,6-diphenylpyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dibenzylpyrazine,
2,5-bis (4-hydroxyphenyl) -3,6-bis (1-phenylethyl) pyrazine, 2,5-bis (4
-Hydroxyphenyl) -3,6-bis (2-phenylethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-bis (1-phenylpropyl) pyrazine, 2,5-bis (4 -Hydroxyphenyl) -3,6
-Bis (2-phenylpropyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-bis (3-phenylpropyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6 -Bis (1-phenylvinyl)
Pyrazine, 2,5-bis (4-hydroxyphenyl)-
3,6-bis (2-phenylvinyl) pyrazine, 2,5
-Bis (4-hydroxyphenyl) -3,6-dinaphthylpyrazine, 2,5-bis (4-hydroxyphenyl)
-3,6-diphenoxypyrazine, 2,5-bis (4-
(Hydroxyphenyl) -3,6-bis (fluoromethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-bis (difluoromethyl) pyrazine,
2,5-bis (4-hydroxyphenyl) -3,6-bis (trifluoromethyl) pyrazine, 2,5-bis (4
-Hydroxyphenyl) -3,6-bis (chloromethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-bis (dichloromethyl) pyrazine, 2,
5-bis (4-hydroxyphenyl) -3,6-bis (trichloromethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-bis (bromomethyl) pyrazine, 2,5-bis (4 -Hydroxyphenyl)-
3,6-bis (dibromomethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-bis (tribromomethyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6 -Difluoropyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dichloropyrazine, 2,5-bis (4-hydroxyphenyl) -3,
6-dibromopyrazine, 2,5-bis (3,5-dimethyl-4-hydroxyphenyl) -3,6-dimethylpyrazine, 2,5-bis (3,5-dimethyl-4-hydroxyphenyl) -3, 6-diethylpyrazine, 2,5-bis (3,5-dimethyl-4-hydroxyphenyl)-
3,6-dipropylpyrazine, 2,5-bis (3,5-
Diphenyl-4-hydroxyphenyl) -3,6-dimethylpyrazine, 2,5-bis (3,5-diphenyl-4)
-Hydroxyphenyl) -3,6-diethylpyrazine,
2,5-bis (3,5-diphenyl-4-hydroxyphenyl) -3,6-dipropylpyrazine, 2,5-bis (3,5-dichloro-4-hydroxyphenyl) -3,
6-dimethylpyrazine, 2,5-bis (3,5-dichloro-4-hydroxyphenyl) -3,6-diethylpyrazine, 2,5-bis (3,5-dichloro-4-hydroxyphenyl) -3, 6-dipropylpyrazine, 2,5-
Bis (3,5-dibromo-4-hydroxyphenyl)-
3,6-dimethylpyrazine, 2,5-bis (3,5-dibromo-4-hydroxyphenyl) -3,6-diethylpyrazine, 2,5-bis (3,5-dibromo-4-hydroxyphenyl)- 3,6-dipropylpyrazine, 2,
5-bis (3-methyl-4-hydroxyphenyl) pyrazine, 2,5-bis (3,5-dimethyl-4-hydroxyphenyl) pyrazine, 2,5-bis (3-phenyl-
4-hydroxyphenyl) pyrazine, 2,5-bis (3,5-diphenyl-4-hydroxyphenyl) pyrazine, 2,5-bis (3-chloro-4-hydroxyphenyl) pyrazine, 2,5-bis (3 , 5-dichloro-4
-Hydroxyphenyl) pyrazine, 2,5-bis (3-
Bromo-4-hydroxyphenyl) pyrazine, 2,5-
Bis (3,5-dibromo-4-hydroxyphenyl) pyrazine is exemplified.

Particularly preferred are 2,5-bis (4-hydroxyphenyl) -3,6-dimethylpyrazine,
5-bis (4-hydroxyphenyl) -3,6-diethylpyrazine, 2,5-bis (4-hydroxyphenyl)
-3,6-dipropylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-methylpyrazine, 2,5-bis (4-hydroxyphenyl) -3-ethylpyrazine,
2,5-bis (3,5-dichloro-4-hydroxyphenyl) pyrazine, 2,5-bis (3,5-dibromo-4)
-Hydroxyphenyl) pyrazine, 2,5-bis (3,
5-Dichloro-4-hydroxyphenyl) -3,6-dimethylpyrazine and 2,5-bis (3,5-dibromo-4-hydroxyphenyl) -3,6-dimethylpyrazine are used.

The reaction of conducting polycondensation in the presence of an acid binder using the above-mentioned carbonyl dihalide, haloformate, carbonate compound or the like as the above-mentioned carbonate-forming compound is usually carried out in a solvent.

The proportion of the carbonate-forming compound used is as follows:
What is necessary is just to adjust suitably considering the stoichiometric ratio (equivalent) of reaction. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing the compound into the reaction system can be suitably employed.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
An alkali metal carbonate such as sodium carbonate or 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, as described above. Specifically, 2 equivalents or a slightly excessive amount of the acid binder is used relative to the total number of moles of the dihydric phenol (III) and the pyrazine compound (IV) to be used (1 mole usually corresponds to 2 equivalents). Preferably, it is used.

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 xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. The interfacial polycondensation reaction may be performed using two types of solvents that do not mix with each other.

In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used.
It is desirable to carry out the reaction by adding a molecular weight regulator such as p-tert-butylphenol or phenylphenol. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.
The reaction is usually performed 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. Usually, the reaction 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.

Further, first, a part of the reaction material comprising dihydric phenol (III) and the pyrazine compound (IV) is reacted with a carbonate-forming compound to form an oligomer, and then the remaining reaction material is added. A two-step method for completing 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.

When the latter transesterification method between dihydric phenol (III) and pyrazine compound (IV) and bisaryl carbonate is used, a melt polycondensation method, a solid phase polycondensation method and the like are preferable. . When performing the melt polycondensation method, the above two or three types of monomers are mixed,
The reaction is performed in a molten state at a high temperature under reduced pressure. The reaction is
The reaction is usually performed at a temperature in the range of 150 to 350 ° C, preferably 200 to 300 ° C. When the solid-phase polycondensation method is performed, the above two or three types of monomers are mixed, and the mixture is heated in a solid state to a temperature equal to or lower than the melting point of the produced polycarbonate copolymer 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 [η _sp / c] of the obtained polycarbonate copolymer can be adjusted to the above range by various methods such as selection of the above reaction conditions and adjustment of the amount of the molecular weight modifier used. Can be. In some cases, the obtained polycarbonate copolymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [ η _sp / c] as a polycarbonate copolymer.

The resulting reaction product (crude product) can be subjected to various post-treatments such as a known separation and purification method and recovered as a polycarbonate copolymer having a desired purity (purity).

When a compound whose molecule is asymmetric is used as the dihydric phenol (III) or the pyrazine compound (IV) in the production of the polycarbonate copolymer, the orientation of the polymer obtained by the polymerization method may be the same. Although it may be random or random, the polycarbonate copolymer of the present invention includes a polycarbonate copolymer in either orientation.

Further, the present invention provides an electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the polycarbonate copolymer of the present invention is used as a binder resin in the photosensitive layer. A photographic photosensitive member is provided.

The electrophotographic photoreceptor of the present invention may be any known electrophotographic photoreceptor of various types as long as the polycarbonate copolymer of the present invention is used as a binder resin in the photosensitive layer. Good, but the photosensitive layer
In a laminated electrophotographic photoreceptor having at least one charge generation layer and at least one charge transport layer, it is preferable to use the binder resin of the charge transport layer.

The laminated electrophotographic photoreceptor may be one in which a charge transport layer is laminated on a charge generation layer in a photosensitive layer, or one in which a charge generation layer is laminated on a charge transport layer. Good. Further, a conductive or insulating protective film may be formed on the surface layer as needed. further,
An adhesive layer for improving the adhesion between the layers or an intermediate layer such as a blocking layer serving as a charge blocking layer may be formed.

In the electrophotographic photoreceptor of the present invention, the polycarbonate copolymer of the present invention may be used alone or in combination of two or more. If desired, other polycarbonates and the like may be contained as a binder resin component as long as the object of the present invention is not impaired. Further, additives such as an antioxidant may be contained.

As the conductive substrate material used for the electrophotographic photoreceptor of the present invention, various materials such as known materials can be used. Specifically, for example, aluminum,
Conductive by coating conductive material such as aluminum, nickel, chromium, palladium, graphite, etc. on metal plate, metal drum or metal sheet, plastic sheet of brass, copper, nickel, steel, etc. by vapor deposition, sputtering, coating etc. It is possible to use a material that has been subjected to a surface treatment, a metal drum surface that has been subjected to a metal oxide treatment by electrode oxidation or the like, or a substrate that has been subjected to a conductivity treatment on a substrate such as glass, plastic plate, cloth, or paper. it can.

The charge generating layer of the multi-layer type electrophotographic photoreceptor has at least a charge generating substance, and the charge generating layer is formed on a substrate as an underlayer by vacuum deposition, sputtering, or the like. Or by forming a layer formed by binding a charge generating substance using a binder resin on a substrate serving as an underlayer. As a method of 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 material is dispersed or dissolved in a suitable solvent together with a binder resin is used. ,
A method in which the composition is applied on a substrate serving as a predetermined base and dried is preferably used.

As the charge generating substance, various substances such as known substances can be used. Specifically, for example, selenium alone such as amorphous selenium and trigonal selenium, and selenium such as selenium-tellurium alloys, selenium compounds such as As ₂ Se ₃ or selenium-containing compositions, zinc oxide, CdS-
Inorganic materials consisting of Group II and Group IV elements such as Se,
Various inorganic materials such as oxide-based semiconductors such as titanium oxide, silicon-based materials such as amorphous silicon, metal or metal-free phthalocyanine, cyanine, anthracene, bisazo compound, pyrene, perylene, pyrylium salt, thiapyrylium salt, polyvinylcarbazole, square Examples include various organic materials such as a lithium pigment.

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

The binder resin in the charge generating layer is not particularly limited, and various resins such as known ones can be used. Specifically, for example, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-acetic acid Vinyl copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate,
Thermoplastic resins such as polyamide, polyketone, polyacrylamide, butyral resin, and polyester, and thermosetting resins such as polyurethane, epoxy resin, and phenol resin can be used.

The polycarbonate copolymer of the present invention can be used as a binder resin in the charge generation layer.

Next, the charge transport layer can be obtained by forming a layer in which a charge transport material is bound on a base substrate using the polycarbonate copolymer of the present invention as a binder resin. it can.

As a method for forming the charge transport layer, various methods such as known methods can be used. Usually, the charge transport material is dispersed or dissolved in an appropriate solvent together with the above-mentioned polycarbonate copolymer. A method of applying a coating liquid on a substrate serving as a predetermined base and drying the coating liquid is used.

In the charge transport layer, the polycarbonate copolymer of the present invention can be used singly or as a mixture of two or more. In addition, other binder resins can be used in combination with the above-mentioned polycarbonate containing a disiloxane unit, as long as the object of the present invention is not impaired.

As the charge transporting substance that can be used in the present invention, for example, there are a conventionally used electron transporting substance and hole transporting substance.

Specific examples of the electron transporting substance include, for example, chloranil, bromanyl, 2,3-dichloro-5,6-
Dicyano-p-benzoquinone, tetracyanoethylene,
Tetracyanoquinodimethane, 2,4,7-trinitro-
9-fluorenone, 2,4,5,7-tetranitro-9
-Fluorenone, 2,4,7-trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone, 2,4,9-trinitrothioxanthone, 3,5-dimethyl-3 ', 5' Electron-withdrawing substances such as -di-tert-butyl-4,4'-diphenoquinone; and those obtained by polymerizing these electron-withdrawing substances. These may be used alone or in a combination of two or more.

As the hole transporting substance, pyrene, N-ethylcarbazole, N-isopropylcarbazole,
-Methyl-N-phenylhydrazino-3-methylidene-
9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N
-Diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3
-Methylidene-10-ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α
-Naphthyl-N-phenylhydrazone, p-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone,
1,3,3-trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 1-phenyl-1,2,3,4- Hydrazones such as tetrahydroquinoline-6-carboxaldehyde-1 ', 1'-diphenylhydrazone, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- ( p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [repidyl (2 )]-3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (5)]-3- (p-diethylaminophenyl)
Pyrazoline, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p
-Diethylaminostyryl) -4-methyl-5- (p-
Diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (α-methyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1-phenyl-3- (p-diethylaminostyryl)- 4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-
pyrazolines such as p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline, 2- (p-diethylaminostyryl) -δ-
Oxazole compounds such as diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole, 2- (p-diethylaminostyryl) -6-diethylaminobenzo A thiazole compound such as thiazole, a triarylmethane compound such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1,1-bis (4-N, N-diethylamino-
Polyarylamines such as 2-methylphenyl) heptane and 1,1,2,2-tetrakis (4-N, N-dimethylamino-2-methylphenyl) ethane; N, N'-diphenyl-N, N ' -Bis (methylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (ethylphenyl) benzidine, N, N'-diphenyl-N, N '
-Bis (propylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (isopropylphenyl) benzidine, N, N ' -Diphenyl-
N, N'-bis (sec-butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (tert
-Benzidine compounds such as -butylphenyl) benzidine and N, N'-diphenyl-N, N'-bis (chlorophenyl) benzidine, butadiene compounds, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene , Polyvinyl acridine, poly-9-vinylphenylanthracene, organic polysilane, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, and the like.

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

Specific examples of the solvent used for forming the charge generation layer and the charge transport layer include, for example, benzene,
Aromatic solvents such as toluene, xylene and chlorobenzene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate and ethyl cellosolve, carbon tetrachloride, chloroform, dichloromethane and tetrachloroethane Halogenated hydrocarbons, ethers such as tetrahydrofuran and dioxane, dimethylformamide, dimethylsulfoxide, diethylformamide and the like.

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

The coating of each layer can be carried out by using various coating apparatuses such as known ones. Specifically, for example, an applicator, a spray coater, a bar coater, a chip coater, a roll coater, a dip coater, a doctor blade, etc. Can be performed.

The photosensitive layer of the single-layer type electrophotographic photosensitive member contains at least the polycarbonate copolymer of the present invention, the above-mentioned charge transporting substance, and the above-mentioned charge transporting substance. As a method for forming the photosensitive layer, various methods such as a known method can be used.In general, for example, a charge generating substance and a charge transporting substance are dispersed or dispersed in a suitable solvent together with the polycarbonate copolymer of the present invention. A method in which a coating liquid obtained by dissolution is applied onto a substrate serving as a predetermined base and dried is preferably used.

In addition, as long as the object of the present invention is not impaired,
Other binder resins can be used in combination with the polycarbonate copolymer of the present invention.

The electrophotographic photoreceptor of the present invention does not cause whitening (gelling) of the coating liquid during its production, and has excellent mechanical properties such as excellent printing durability even when used repeatedly for a long time. An electrophotographic photoreceptor that is extremely excellent in practical use and maintains strength and electrophotographic properties, and can be suitably used in various electrophotographic fields.

[0059]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1-1) D (-)-p-hydroxyphenylglycine (200 g) was suspended in acetic anhydride (500 ml) and pyridine (100 ml) and heated at 100 ° C. for 2 hours. The solvent was distilled off to obtain 1-acetylamino-1- (4-acetoxyphenyl) -2-propanone (described below).

[0061]

Embedded image ¹ H-NMR (CDCl_Three) Δ = 1.99 (3H, s),
2.12 (3H, s), 2.29 (3H, s), 5.5
6 (1H, d, J = 6.5 Hz), 6.8 (1H, b
rd, NH), 7.10, 7.34 (each 2
H, AA'BB ') ppm

(1-2) 1-acetylamino-1-
(4-Acetoxyphenyl) -2-propanone was dissolved in concentrated hydrochloric acid (250 ml) and heated at 120 ° C. for 12 hours. The solvent was distilled off to obtain 1-amino-1- (4-hydroxyphenyl) -2-propanone hydrochloride (described below).

[0063]

Embedded image ¹ H-NMR (CD_ThreeOD) δ = 2.11 (3H, s),
5.22 (1Hs), 6.91, 7.29 (eac
h 2H, AA′BB ′) ppm (1-3) 1-amino-1- (4-hydroxyphenyl)
) -2-propanone hydrochloride in methanol (200 m
l), and add ammonia water (300 ml) to this.
And stirred at room temperature for 8 hours. Suction filtration of generated precipitate
And suspended in methanol (500 ml).
% Hydrogen peroxide (200 ml) and stirred at room temperature for 8 hours.
Stirred. The generated 2,5-bis (4-hydroxyphenyl)
L) 110 g of 3,6-dimethylpyrazine (described below) was obtained.
Was.

[0064]

Embedded image ¹ H-NMR (CD_ThreeOD + NaOD) δ = 2.59 (6
H, s), 6.76, 7.31 (each 4H, A
A'BB ') ppm

(1-4) 74 g of 2,2-bis (4-hydroxyphenyl) propane was dissolved in 550 ml of a 6% aqueous sodium hydroxide solution, and 250 ml of methylene chloride was added. While cooling the obtained solution, phosgene gas was blown at a rate of 950 ml / min for 15 minutes under cooling.
The reaction solution was allowed to stand, and the organic layer was separated.
Having a chloroformate group at the molecular end,
A methylene chloride solution of the oligomer of 2-bis (4-hydroxyphenyl) propane was obtained.

To the resulting oligomer solution, a small amount of p-tert-butylphenol and methylene chloride were added as terminal stoppers to make a total volume of 720 ml, and then 2,5-bis (4-hydroxyphenyl) -3,6- 20 g of dimethylpyrazine is 240 ml of 1.5 N potassium hydroxide aqueous solution
, And 5 ml of a 5% aqueous solution of triethylamine was added thereto, followed by vigorous stirring at room temperature for 1 hour. Add 1 liter of methylene chloride and 1.5 parts of water to the reaction product.
After adding 1 liter and stirring, the aqueous layer was separated, and the organic phase was washed once with 0.01 N hydrochloric acid and three times with water. This organic phase was dropped into methanol to obtain 81.5 g of a polycarbonate copolymer.

The polycarbonate copolymer thus obtained had a concentration of 0.5 g / methylene chloride as a solvent.
dl solution at 20 ° C. [η _sp / c] is 0.
It was 875 dl / g. The result of ¹ H-NMR spectrum analysis of this polycarbonate copolymer was 1.70.
(6H, s), 2.66 (1.06H, s), 7.1-
7.25 (4H, m), 7.25 to 7.35 (4H,
m), 7.40 (0.70 H, dm, J = 9 Hz),
7.73 (0.70 H, dm, J = 9 Hz) (all in ppm). As a result of IR spectrum analysis, 3030 cm ^-1, 1590 cm ^-1, absorption of the benzene ring to 830 cm ^-1, absorption by carbonyl group 1650 cm ^-1, absorption was observed by an ether bond to 1240 cm ^-1, carbonate linkages It was found to have. From the above results, it was confirmed that the obtained polycarbonate copolymer was composed of the following repeating units.

[0068]

Embedded image

Example 2 Example 1 was repeated except that 87 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used instead of 74 g of 2,2-bis (4-hydroxyphenyl) propane used in Example 1. The same operation was performed to obtain 83 g of a polycarbonate copolymer.

The thus obtained polycarbonate copolymer had a concentration of 0.5 g / methylene chloride in a solvent.
dl solution at 20 ° C. [η _sp / c] is 0.
It was 894 dl / g. When the structure and composition of this polycarbonate copolymer were confirmed by IR spectrum analysis, the same absorption as in Example 1 was observed, and it was confirmed that the polycarbonate copolymer had the following structure.

[0071]

Embedded image

Example 3 (3-1) Acetic anhydride (500) of (1-1) of Example 1
ml) was replaced with propionic anhydride (550 ml) in the same manner as in (1-1) of Example 1 to obtain 1-propionylamino-1- (4-propionyloxyphenyl)-
2-butanone (described below) was obtained.

[0073]

Embedded image ¹ H-NMR (CDCl_Three) Δ = 1.00 (3H, t, J
= 7 Hz), 1.08 (3H, t, J = 7 Hz), 1.
25 (3H, t, J = 7 Hz), 2.24 (2H, q,
J = 7 Hz), 2.43 (2H, q, J = 7 Hz),
2.58 (2H, q, J = 7 Hz), 5.58 (1H,
d, J = 6.5 Hz), 6.8 (1H, br d, N
H), 7.08, 7.31 (each 2H, AA'B
B ') ppm

(3-2) 1- of (1-2) of Example 1
Acetylamino-1- (4-acetoxyphenyl) -2
-Propanone was changed to 1-propionylamino-1- (4-propionyloxyphenyl) -2-butanone in the same manner as (1-2) of Example 1 to obtain 1-amino-
1- (4-Hydroxyphenyl) -2-butanone hydrochloride (described below) was obtained.

[0075]

Embedded image ¹ H-NMR (CD_ThreeOD) δ = 1.00 (3H, t, J
= 7 Hz), 2.43 (2H, qd, J = 7.2H)
z), 5.17 (1H, s), 6.89, 7.24 (e
ach 2H, AA'BB ') ppm

(3-3) 1 of (1-3) of the first embodiment
(1-3) of Example 1 except that -amino-1- (4-hydroxyphenyl) -2-propanone hydrochloride was changed to 1-amino-1- (4-hydroxyphenyl) -2-butanone hydrochloride. And 3,6-diethyl-2,5-
Bis (4-hydroxyphenyl) pyrazine (described below)
15 g were obtained.

[0077]

Embedded image ¹ H-NMR (CD_ThreeOD + NaOD) δ = 1.21 (6
H, t, J = 7 Hz), 2.91 (4H, q, J = 7)
 Hz), 6.75, 7.26 (each 4H, A
A'BB ') ppm

(3-4) Instead of 20 g of 2,5-bis (4-hydroxyphenyl) -3,6-dimethylpyrazine used in Example 1, 2,5-bis (4-hydroxyphenyl) -3, The same operation as in Example 1 was performed except that 22 g of 6-diethylpyrazine was used, to obtain 85 g of a polycarbonate copolymer.

The polycarbonate copolymer thus obtained had a concentration of 0.5 g / methylene chloride as a solvent.
dl solution at 20 ° C. [η _sp / c] is 0.
It was 912 dl / g. When the structure and composition of this polycarbonate copolymer were confirmed by IR spectrum analysis, the same absorption as in Example 1 was observed, and it was confirmed that the polycarbonate copolymer had the following structure.

[0080]

Embedded image

Example 4 In 600 ml of a 3N aqueous sodium hydroxide solution,
A solution in which 36.5 g of 2,5-bis (4-hydroxyphenyl) -3,6-dimethylpyrazine and 28.5 g of 2,2-bis (4-hydroxyphenyl) propane are dissolved,
And 250 ml of methylene chloride were introduced into a 1 liter flask. The reaction solution was vigorously stirred while maintaining the liquid temperature around 10 ° C. by external cooling, and phosgene gas was added at 340 ml /
Minutes were blown for 30 minutes. Thereafter, stirring was continued for 1 hour to complete the polymerization. After completion of the reaction, the organic phase was diluted by adding 500 ml of methylene chloride, washed with water, diluted hydrochloric acid and water in that order, and then poured into methanol to obtain 60 g of a polycarbonate copolymer having the following structure.

[0082]

Embedded image The polycarbonate copolymer thus obtained is
The reduced viscosity [η _sp / c] at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent is 1.21 dl / g.
Met.

Example 5 Using a hydrazone derivative having the following structure as a charge transporting material, a solution of a charge transporting material: the polycarbonate copolymer of Example 1: methylene chloride = 1: 1: 8 (weight ratio) was prepared and coated. It was a working liquid. Even if this coating liquid is left for one month,
No cloudiness or gelation was observed. This coating solution is applied by dip coating on a charge generation layer (thickness: about 20 μm) made of oxotitanium phthalocyanine formed on an aluminum conductive substrate, and dried to form a charge transport layer (thickness: 0.1 μm). Then, a laminated electrophotographic photosensitive member was produced. During the coating, the charge transport layer did not crystallize.

The evaluation of the electrophotographic characteristics of the obtained laminated electrophotographic photoreceptor was carried out using an electrostatic charging tester EPA-8100.
Using (Kawaguchi Electric Co., Ltd.), a corona discharge of -6 kV was performed, and an initial surface potential (V ₀ ), a residual potential (V _R ) after light irradiation (5 seconds), and a half reduction exposure (E _{1 /). 2} ) was measured and performed. Table 1 shows the results.

The abrasion resistance of the charge transport layer was evaluated by using a Suga abrasion tester to reciprocate the sample 1200 times on abraded paper with a load of 200 g and measuring the abrasion amount. Table 2 shows the results. Charge transport material (1-phenyl-1,2,3,4-tetrahydroquinoline-6-carboxaldehyde-1 ′,
1'-diphenylhydrazone)

[0086]

Embedded image

Example 6 A laminated electrophotographic photosensitive member was produced in the same manner as in Example 5, except that the polycarbonate copolymer obtained in Example 2 was used. The evaluation results of the stability of the coating liquid and the crystallinity during coating were the same as in Example 5. Tables 1 and 2 show the evaluation results of the electrophotographic characteristics and the wear resistance, respectively.

Example 7 A laminated electrophotographic photosensitive member was produced in the same manner as in Example 5, except that the polycarbonate copolymer obtained in Example 3 was used. The evaluation results of the stability of the coating liquid and the crystallinity during coating were the same as in Example 5. Tables 1 and 2 show the evaluation results of the electrophotographic characteristics and the wear resistance, respectively.

Example 8 A laminated electrophotographic photosensitive member was produced in the same manner as in Example 5 using the polycarbonate copolymer obtained in Example 4. The evaluation results of the stability of the coating liquid and the crystallinity during coating were the same as in Example 5. Tables 1 and 2 show the evaluation results of the electrophotographic characteristics and the wear resistance, respectively.

Comparative Example 1 A commercially available polycarbonate having the following structure ([η _sp /c]=0.78 dl / g) produced using 2,2-bis (4-hydroxyphenyl) propane as a monomer material was used. A laminated electrophotographic photosensitive member was produced in the same manner as in Example 5. As a result, the coating liquid became cloudy on the second day, and a gel was generated. At the time of coating, a part of the charge transport layer crystallized (whitened). Tables 1 and 2 show the electrophotographic characteristics and abrasion resistance of the obtained laminated electrophotographic photosensitive member.

[0091]

Embedded image

Comparative Example 2 In place of 74 g of 2,2-bis (4-hydroxyphenyl) propane of (1-4) in Example 1, 1,1-bis (4
-Hydroxyphenyl) cyclohexane 87 g
The same operation as in Example 1 was performed except that 35 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used instead of 20 g of 5-bis (4-hydroxyphenyl) -3,6-dimethylpyrazine, and the following structure was used. Was obtained ([η _sp /c]=0.84 dl / g). Using this polycarbonate, a laminated electrophotographic photosensitive member was produced in the same manner as in Example 1. The results of evaluating the stability of the coating solution and the crystallization during coating were the same as in Example 5. Tables 1 and 2 show the electrophotographic characteristics and abrasion resistance of the obtained laminated electrophotographic photosensitive member.
It was shown to.

[0093]

Embedded image

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

According to the present invention, there is provided an electrophotographic photoreceptor which can be suitably used as a binder resin in a photosensitive layer of an electrophotographic photoreceptor, has good electrophotographic properties and is excellent in printing durability. An excellent polycarbonate that can be easily realized, and a polycarbonate copolymer having a novel structure that can be suitably used in various polymer material application fields such as electrophotographic photoreceptors and EL element production is obtained. .
Further, according to the production method of the present invention, the polycarbonate copolymer of the present invention can be suitably produced. Further, according to the present invention, it is possible to obtain an electrophotographic photoreceptor that maintains excellent printing durability and good electrophotographic characteristics over a long period.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideyuki Miyamoto 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd. (56) References Journal of Organic Chemistry; vol. 49 (No. 25) p4755-4760 (1984) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 G03G 5/05 101 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (I) [Wherein, R ¹ and R ² are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. There, a and b are each independently an integer of 0 to 4, X is a single bond, -O -, - S -, - SO -, - SO 2
—, —CR ³ R ⁴ — (where R ³ and R ⁴ are each independently
It is a hydrogen atom, a trifluoromethyl group, a C1-C6 alkyl group, or a C6-C12 substituted or unsubstituted aryl group. ), A 1,1-cycloalkylene group having 5 to 11 carbon atoms or an α, ω-alkylene group having 2 to 10 carbon atoms. And a repeating unit (I) represented by the following general formula (II): Wherein R ⁵ is a halogen atom, an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ⁶ is an alkyl group having 1 to 30 carbon atoms, A halogenated alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 1 to 30 carbon atoms, an alkenyl group or alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom, Is 0
Is an integer of 4, and d is an integer of 0 to 2, provided that both c and d are not 0. And the content of the repeating unit (II) is 0.01 in a molar ratio of the repeating unit (II) to the total of the repeating unit (I) and the repeating unit (II). ~
0.9, and 0.5 g / d using methylene chloride as a solvent.
A polycarbonate copolymer having a reduced viscosity [η _sp / c] at 20 ° C. of a 1-concentration solution of 0.3 dl / g or more. 2. The following general formula (III): [Wherein, R ¹ and R ² are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. There, a and b are each independently an integer of 0 to 4, X is a single bond, -O -, - S -, - SO -, - SO 2
—, —CR ³ R ⁴ — (where R ³ and R ⁴ are each independently
It is a hydrogen atom, a trifluoromethyl group, a C1-C6 alkyl group, or a C6-C12 substituted or unsubstituted aryl group. ), A 1,1-cycloalkylene group having 5 to 11 carbon atoms or an α, ω-alkylene group having 2 to 10 carbon atoms. And a dihydric phenol (III) represented by the following general formula (IV): Wherein R ⁵ is a halogen atom, an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ⁶ is an alkyl group having 1 to 30 carbon atoms, A halogenated alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 1 to 30 carbon atoms, an alkenyl group or alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom, Is 0
Is an integer of 4, and d is an integer of 0 to 2, provided that both c and d are not 0. The method for producing a polycarbonate copolymer according to claim 1, wherein the pyrazine compound (IV) is reacted with a carbonate-forming compound. 3. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the polycarbonate polymer according to claim 1 is used as a binder resin of the photosensitive layer.