JPH11279273A - Polycarbonate resin and its production and electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin capable of giving molded products having excellent optical properties, electrical properties, mechanical properties, and especially abrasion resistance by including repeating units bound to the residues of an imine compound having a specific structure in repeating units constituting the subject polycarbonate resin. SOLUTION: This polycarbonate resin has repeating units of formulae I and II R<1> and R<2> are each hydrogen, a 1-12C alkyl or the like; (s) is 0-4; Y is a group of formula III or IV [R<3> is a halogen, a 1-12C alkoxy or the like; (a) is 1 or 2; R<4> and R<5> are each hydrogen, a 6-18C aryl or the like; (r) is 0-4; (b) is 1-12]; Ar is a group of formula V or VI [X is a single bond, O or the like; R<6> is hydrogen, trifluoromethyl or the like; (m) is 0-4; (q) is 0-6] or the like} in a unit I/(unit I + unit II) molar ratio of 0.001-1. The resin preferably has a reducing viscosity of 0.3-4 dl/g measured in a concentration of 0.5 g/dl in methylene dichloride at 20 deg.C. The resin is obtained by reacting a dihydroxyimine compound giving the unit of formula I with a carbonate ester- forming compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin having excellent mechanical properties, optical properties and electrophotographic properties, a method for producing the same, and durability including the polycarbonate resin as a binder resin in a photosensitive layer. It relates to an excellent electrophotographic photoreceptor.

[0002]

2. Description of the Related Art Polycarbonate resins have been used as materials for molded articles in various industrial fields because of their excellent mechanical properties, thermal properties and electrical properties. recent years,
Further, they are also frequently used in the field of functional products utilizing the optical properties of the polycarbonate resin. With the expansion of such application fields, the required performance for the polycarbonate resin has been diversified. In order to respond to such a demand, it is necessary to use only a conventionally used polycarbonate resin made from 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, or the like alone. Because of insufficient support, polycarbonate resins having various chemical structures have been proposed.
However, since there are specific characteristics required for various applications, development of a polycarbonate resin having performance satisfying those requirements is required.

As such a functional product, there is an organic electrophotographic photosensitive member in which a photosensitive layer using a polycarbonate resin as a binder resin for an organic charge generation material or a charge transport material is formed on a conductive substrate. As the electrophotographic photoreceptor, conventionally, one using an inorganic photoconductive material such as selenium or α-silicon has been used, but recently, since the performance of the organic electrophotographic photoreceptor has been improved, Its use rate is expanding.

[0004] The organic electrophotographic photosensitive member is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process to be applied. In this electrophotographic photoreceptor, operations such as corona charging or contact charging, toner development, transfer to paper, and cleaning treatment are repeatedly performed on the surface of the photosensitive layer. External force is applied. Therefore, in order to maintain the image quality of electrophotography over a long period of time, the photosensitive layer provided on the surface of the electrophotographic photoreceptor is required to have durability against these external forces.

In order to meet such demands, as a binder resin for an organic electrophotographic photoreceptor, a polycarbonate resin having good compatibility with a charge transporting material used in a photosensitive layer and excellent optical characteristics has been used. However, in the case of using the conventionally known polycarbonate resin, the durability of the electrophotographic photosensitive member has not been sufficiently satisfied.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to obtain a molded article having excellent optical, electrical, and mechanical properties, and especially excellent wear resistance. Polycarbonate resin and its production method,
Another object of the present invention is to provide an electrophotographic photoreceptor excellent in durability containing the polycarbonate resin as a binder resin.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a repeating unit constituting a polycarbonate resin is provided with a residue of an imine compound having a specific chemical structure. The inventors have found that a polycarbonate resin having a repeating unit in a bonded form is excellent in electrical properties, mechanical properties, and especially abrasion resistance, and have completed the present invention based on these findings.

That is, the gist of the present invention is as follows. (1) A repeating unit represented by the following general formula [1] (1)
And the molar ratio of the repeating unit (1) to the total of the repeating unit (1) and the repeating unit (2) [(1) / ((1) + ( 2)))
Is a polycarbonate resin having a ratio of 0.001 to 1.

[0009]

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[R ¹ and R ² in the formula [1] represent a hydrogen atom,
An alkyl group which may have a substituent having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 6 to 18 carbon atoms
Represents a condensed polycyclic hydrocarbon group, s represents an integer of 0 to 4, Y represents the following general formula [3] or [4],

[0011]

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(R ³ in the formula [3] is a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an alkyl group which may have a substituent having 1 to 12 carbon atoms, A represents an aryl group or a condensed polycyclic hydrocarbon group having 6 to 18 carbon atoms, a represents 1 or 2, and R ⁴ R ⁵ in the formula [4] each independently represents a hydrogen atom, a carbon number of 1 to 12; An alkyl group of
Represents a trifluoromethyl group or an aryl group having 6 to 18 carbon atoms, r represents an integer of 0 to 4, b represents an integer of 1 to 12), and Ar in the formula [2] represents The following general formulas [5a] to [5d],

[0013]

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(X in the formula [5a] is a single bond, -O-,
-CO-, -S-, -SO-, -SO _Two-, -CR⁸R
⁹-(However, R⁸, R⁹Are each independently a hydrogen atom or carbon
An alkyl group of the formulas 1 to 12 or a trifluoromethyl group
A) substituted or unsubstituted cycloalkyl having 6 to 12 carbon atoms
Alkylidene group, substituted or unsubstituted having 2 to 12 carbon atoms
Α, ω-alkylene group of 9,9-fluorenylidene
Group, 1,8-menthanediyl group, 2,8-menthanediyl
Group, substituted or unsubstituted pyradylidene group or carbon
Represents a substituted or unsubstituted arylene group of Formulas 6 to 24
And R in the formulas [5a] to [5d]⁶, R⁷Are independent
A hydrogen atom, an alkyl group having 1 to 12 carbon atoms or trif
Fluoromethyl group, alkoxy group having 1 to 12 carbon atoms, carbon
An alkyl group which may have a substituent of Formulas 1 to 12, carbon
A substituted or unsubstituted aryl group having a prime number of 6 to 18 or
C6-C12 substituted or unsubstituted aryloxy
M represents an integer of 0 to 4; q represents 0 to 6;
An integer, n is an integer of 0 to 200, and p is each independently 0 to 6.
Represents an integer) or (2) using methylene chloride as a solvent in an amount of 0.5 g / d
Reduced viscosity measured at a temperature of 20 ° C. [η_SP/
c) is at least 0.1 deciliter / g
The polycarbonate resin according to (1). (3) Dihydroxyimine represented by the following general formula [6]
Compound alone or with the dihydroxyimine compound
A dihydroxy compound represented by the following general formula [7]:
Characterized by reacting with a carbonate-forming compound
The polycarbonate resin according to the above (1) or (2),
Manufacturing method.

[0015]

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[0016] [R ^1, R ^2, Y, s in the formula (6) has the same meaning as R ^1, R ^2, Y, s of the formula [1] in,
Ar in the formula [7] has the same meaning as Ar in the formula [2]. (4) In an electrophotographic photoreceptor having at least a photosensitive layer on a conductive substrate, the photosensitive layer may have the above (1) An electrophotographic photoreceptor comprising the polycarbonate resin described above.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the polycarbonate resin of the present invention, a repeating unit constituting the polycarbonate resin is a polymer consisting of the repeating unit (1) represented by the general formula [1] or a compound represented by the general formula [1]. A copolymer comprising a repeating unit (1) represented by the general formula (2) and a repeating unit (2) represented by the general formula (2), wherein the polymer chain has any of a linear, branched or cyclic structure. It may have a specific terminal structure or a special branched structure.

[0018] These formulas (1) and a polycarbonate resin comprising a repeating unit represented by (2), Still more particularly, R ¹ in the formula (1), R ²
Examples of the alkyl group which may have a substituent having 1 to 12 carbon atoms represented by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-butyl group, a t-butyl group, Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
A dodecyl group and the like; and the aryl group having 6 to 18 carbon atoms include a phenyl group, a tolyl group, a styryl group, a biphenylyl group, and a naphthyl group.
As the condensed polycyclic hydrocarbon group of 8, a carbazolyl group,
Examples include a pyrazoline group, a pyrene group, and an imidazolyl group.

Further, R in the above formula [3]^ThreeThe charcoal represented by
Examples of the alkoxy group having a prime number of 1 to 12 include a methoxy group,
Toxic group, propoxy group, isopropoxy group, butoxy
Group, isobutoxy group, 2-butoxy group, t-butoxy group
Group, pentyloxy group, hexyloxy group, heptyloxy
Xyl, octyloxy, nonyloxy, decylio
Xy, undecyloxy, dodecyloxy, etc.
And may have a substituent having 1 to 12 carbon atoms.
Examples of the alkyl group include R in the above formula [1]. ¹Is a table
The same as the alkyl group, aryl having 6 to 18 carbon atoms
The groups include phenyl, tolyl, styryl, bif
Enylyl group, naphthyl group, etc., having 6 to 1 carbon atoms.
As the condensed polycyclic hydrocarbon group of 8, the above-mentioned formula [1]
R¹The same as the condensed polycyclic hydrocarbon group represented by
I can do it.

The formulas [4] and [5a] to [5]
d) an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 6 to 18 carbon atoms represented by R ^{4 to} R ^{9 in}
As the aryl group, there can be mentioned the same as the respective groups represented by R ¹ in the formula [1]. Also,
Examples of the substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms represented by R ⁶ and R ⁷ include a phenoxy group, a tolyloxy group, a styryloxy group, a naphthyloxy group, and a biphenyloxy group.

The substituted or unsubstituted cycloalkylidene group having 6 to 12 carbon atoms represented by X in the formula [5a] includes cyclohexylidene group, cycloheptylidene group, cyclooctylidene group and cyclononylidene group. , Cycloundecylidene group, etc., having 1 to 12 carbon atoms.
Examples of the substituted or unsubstituted α, ω-alkylene group include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group and the like. Examples of the substituted or unsubstituted arylene group having 6 to 24 carbon atoms include a phenyl group, a naphthylene group, a biphenylene group, and a terphenylene group.

When the copolymer is composed of the repeating unit (1) and the repeating unit (2), the molar ratio of the repeating unit (1) [(1) / ((1) + (2)) 〕But,
Those having a value of 0.01 or more, preferably those having a range of 0.1 to 0.7 are suitably used. This molar ratio is
If it is less than 0.01, the effect of improving photoconductivity and mechanical strength cannot be sufficiently obtained.

In addition to the repeating units (1) and (2), structural units other than those defined by the above formulas (1) and (2) may be used in the polycarbonate resin as long as the object of the present invention is not impaired. Or a unit having a polyester unit, a unit having a polyester, polyurethane, polyether, or polysiloxane structure.

This polycarbonate resin has a concentration of 0.5 g / deciliter using methylene chloride as a solvent at 20 ° C.
Reduced viscosity [η _SP / c] measured at a temperature of 0.01 to 5
Those having a deciliter / g, preferably 0.2 to 5 deciliter / g, more preferably 0.3 to 4 deciliter / g are suitably used. This reduced viscosity [η _SP /
If c) is less than 0.01 deciliters / g, the mechanical strength is not sufficient, and when used as a binder resin for an electrophotographic photosensitive member, sufficient printing durability cannot be exhibited. On the other hand, if the reduced viscosity exceeds 5 deciliters / g, the moldability may be reduced.

Next, with respect to the method for producing the polycarbonate resin having the repeating unit, the dihydroxy compound represented by the general formula [6] may be used alone or in combination with the compound represented by the general formula [7]. Dihydroxy compound in a solvent in the presence of an acid acceptor or a catalyst,
By reacting with a carbonate-forming compound,
Can be manufactured.

As the dihydroxy compound represented by the general formula [6], the following compounds can be exemplified as specific compounds.

[0027]

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These dihydroxy compounds may be used alone or as a mixture of two or more. Examples of the dihydroxy compound represented by the general formula [7] include 4,4′-dihydroxybiphenyl,
3,3'-difluoro-4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'- 4,4′-dihydroxybiphenyls such as dihydroxy-3,3′-dicyclohexylbiphenyl; bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) phenylmethane;
Bis (3-methyl-4-hydroxyphenyl) methane,
Bis (3-nonyl-4-hydroxyphenyl) methane,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3-fluoro-4) -Hydroxyphenyl) methane, bis (2-tert-butyl-4-hydroxyphenyl) phenylmethane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenyl) methane, bis (2-hydroxy-4)
Methylphenyl) methane, bis (2-hydroxy-4-
Methyl-6-tert-butylphenyl) methane, bis (2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane, 1,
1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) ) -1-Phenylethane, 2- (4-hydroxy-3-methylphenyl) -2
-(4-hydroxyphenyl) -1-phenylethane,
1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1-phenyl-1,1
-Bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-4-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 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-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 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 (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-
Bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5 -Difluorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (3-bromo-
4-hydroxy-5-chlorophenyl) propane, 2,
2-bis (4-hydroxyphenyl) -1,1,1,
3,3,3-hexafluoropropane, 2,2-bis (2-hydroxy-4-sec-butylphenyl) propane, 2,2-bis (2-hydroxy-4,6-dimethylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2,2- (3-methyl-4-hydroxyphenyl) butane 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (2 -T
tert-butyl-4-hydroxy-5-methylphenyl) -2-methylpropane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,
1-bis (2-tert-butyl-4-hydroxy-5
-Methylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-pentylphenyl)
Butane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) butane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,
1-bis (4-hydroxyphenyl) -3-methylbutane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl ) Heptane, 2,2-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) Nonane, 2,2-bis (4
-Hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (3- Cyclohexyl-4-hydroxyphenyl) cyclohexane,
1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3-methyl-4-hydroxyphenyl)
Bis (hydroxyphenyl) alkanes such as -3,3,5-trimethylcyclohexane; bis (4-hydroxyphenyl) ether such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether Bis (4-hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl- Bis (4-hydroxyphenyl) sulfoxides such as 4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl)
Bis (4-hydroxyphenyl) sulfones such as sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone; bis (such as 4,4′-dihydroxybenzophenone) 4-hydroxyphenyl) ketones;
9,9-bis (4-hydroxyphenyl) fluorene,
9,9-bis (3-methyl-4-hydroxyphenyl)
Bis (hydroxyphenyl) fluorenes such as fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene; dihydroxy-p-terphenyls such as 4,4 "-dihydroxy-p-terphenyl;
Dihydroxy-p-quarterphenyls such as 4,4 ″ ′-dihydroxy-p-quarterphenyl;
5-bis (4-hydroxyphenyl) pyrazine, 2,5
-Bis (4-hydroxyphenyl) -3,6-dimethylpyrazine, 2,5-bis (4-hydroxyphenyl)-
Bis (hydroxyphenyl) pyrazines such as 2,6-diethylpyrazine; 1,8-bis (4-hydroxyphenyl) menthane, 2,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (3- Bis (hydroxyphenyl) menthanes such as methyl-4-hydroxyphenyl) menthane and 1,8-bis (4-hydroxy-3,5-dimethylphenyl) menthane; 1,4-bis [2
-(4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis [2- (4-hydroxyphenyl)-
Bis [2- (4-hydroxyphenyl) -2-propyl] benzenes such as 2-propyl] benzene; 1,3-
Dihydroxynaphthalenes such as dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; dihydroxybenzenes such as resorcin, hydroquinone and catechol;
α, ω-dihydroxypolydimethylsiloxane, α, ω
Polysiloxanes such as -bis [3- (2-hydroxyphenyl) propyl] polydimethylsiloxane;
1,8,8-tetrahydro-1,8-dihydroxyperfluorooctane, 1,1,6,6-tetrahydro-
And dihydroperfluoroalkanes such as 1,6-dihydroxyperfluorohexane.

Among these various dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1- Bis (4-hydroxyphenyl) -1-
Phenylethane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dibromo -4-
Hydroxyphenyl) propane, 3,3-bis (4-hydroxyphenyl) pentane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-
Hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxy-3
-Methoxyphenyl) 1,1,1,3,3,3-hexafluoropropane, α, ω-bis [3- (2-hydroxyphenyl) propyl] polydimethylsiloxane, resorcinol, 2,7-dihydroxynaphthalene, etc. Preferred is 2,2-bis (4-hydroxyphenyl) propane. These dihydroxy compounds may be used alone or as a mixture of two or more.

As the solvent, those used in the production of ordinary polycarbonate resins are used. Specific examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, methylene chloride, chloroform, and the like.
1.1-dichloroethane, 1,2-dichloroethane,
1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,
Suitable examples include halogenated hydrocarbons such as 1,2,2-tetrachloroethane, pentachloroethane, and chlorobenzene, and acetophenone. These solvents may be used alone or in combination of two or more. Furthermore, an interfacial polycondensation reaction may be performed using two kinds of solvents that are not mixed with each other.

Examples of the acid acceptor include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; A base or a mixture thereof can be used. The proportion of the acid binder used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, one equivalent or more, preferably 1 to 5 equivalents of an acid binder may be used per 1 mol of hydroxyl groups of the starting dihydric phenol.

The catalyst includes trimethylamine, triethylamine, tributylamine, N, N-
Dimethylcyclohexylamine, pyridine, tertiary amines such as dimethylaniline, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride,
Quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide, and quaternary phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide are preferred.

Further, as the above-mentioned carbonate-forming compound, various carbonyl halides such as phosgene, haloformates such as chloroformate, carbonate compounds and the like can be used. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably employed. The proportion of the carbonate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

For adjusting the molecular weight of the polycarbonate resin of the present invention, a monovalent carboxylic acid and its derivative or a monovalent phenol can be used as a terminal stopper. For example, p-tert-butyl-phenol, p
-Phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, p-tert-perfluorobutylphenol, 1- (P-hydroxy Benzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3-hexafluoropropyl] phenol, 3,5-bis (perfluorohexyl) Oxycarbonyl) phenol, p-
Perfluorododecyl hydroxybenzoate, p- (1
H, 1H-perfluorooctyloxy) phenol,
2H, 2H, 9H-perfluorononanoic acid, 1,1,
1,3,3,3-tetrafluoro-2-propanol and the like are preferably used.

When producing a branched polycarbonate resin, various branching agents can be used. Specific examples of such a branching agent include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,6-
Dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,4,6-
Tris (4-hydroxyphenyl) heptane, 1,3
5-tris (2-hydroxyphenyl) benzene, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4- Screw [2-
Bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4 -Dihydroxyphenyl)
Propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4-hydroxyphenylisopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis (3
-Methyl-4-hydroxyphenyl) -2-oxo-
Suitable examples include 2,3-dihydroindole, 3,3-bis (4-hydroxyaryl) oxindole, 5-chloroisatin, 5,7-dichloroisatin, and 5-bromoisatin.

Further, if desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added to the reaction system. Next, regarding the reaction conditions when performing the polycondensation reaction, the reaction temperature is usually 0 to 150.
° C, preferably 5 to 40 ° C, and the reaction pressure may be any of reduced pressure, normal pressure, and pressurized pressure. However, the reaction can be usually performed under normal pressure or a pressure of about the self-pressure of the reaction system. The reaction time depends on the reaction temperature, but is 0.5 minutes to
It is 10 hours, preferably about 1 minute to 2 hours. In addition, this reaction may be performed by any of a continuous method, a semi-continuous method, and a batch method.

The molecular weight of the polycarbonate resin can be adjusted within the above-mentioned numerical range of the reduced viscosity by, for example, selecting the reaction conditions and increasing or decreasing the amount of the terminal terminating agent or the branching agent. In some cases, the obtained polycarbonate resin is subjected to physical treatment (mixing, fractionation, etc.).
Or a chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate resin having a desired reduced viscosity.

The polycarbonate resin obtained by this polycondensation reaction can be obtained as a high-purity polycarbonate resin by a known separation and purification method. The polycarbonate resin thus obtained has photoconductivity, and is excellent in heat resistance and mechanical strength, particularly in abrasion resistance. It can be used as a highly useful material in application fields such as electric equipment, electronic equipment, and optical equipment. Also in these application fields, it is suitably used particularly as a binder resin for an electrophotoreceptor. Next, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor in which a photosensitive layer is provided on a conductive substrate, and the photosensitive layer has a surface layer containing the above polycarbonate resin.

The structure of the electrophotographic photoreceptor of the present invention is not particularly limited as long as such a photosensitive layer is formed on a conductive substrate. In addition to the electrophotographic photoreceptor of the above type, any type may be used. Usually, a laminated electrophotographic photoreceptor in which the photosensitive layer has at least one charge generation layer and at least one charge transport layer forming a surface layer is preferable, and the above polycarbonate is contained in at least one charge transport layer. Preferably, a resin is used as a binder resin and / or as the surface protective layer.

When the above-mentioned polycarbonate resin is used as a binder resin in the electrophotographic photoreceptor of the present invention, the polycarbonate resin may be used alone or in combination of two or more. A composition containing a resin component such as another polycarbonate resin may be used as long as the object of the invention is not hindered.

As the conductive substrate used in the electrophotographic photoreceptor of the present invention, various substrates such as known ones can be used. Specifically, aluminum, nickel, chromium, palladium, titanium, molybdenum, indium,
Gold, platinum, silver, copper, zinc, brass, stainless steel, lead oxide,
Plates, drums, and sheets made of tin oxide, indium oxide, ITO, or graphite; and films, sheets, and seamless belts of glass, cloth, paper, or plastic that have been subjected to conductive treatment such as coating by vapor deposition, sputtering, or coating; and aluminum. Plastic film with laminated metal foil such as
A sheet and a seamless belt, a film-like sheet and a seamless belt of a metal plate, a metal drum which has been subjected to metal oxidation treatment by electrode oxidation or the like can be used.

The charge generation layer of the multi-layer type electrophotographic photoreceptor contains at least a charge generation substance, and the charge generation layer is formed on a substrate as an underlayer by a vacuum evaporation method, a chemical evaporation method, or a sputtering method. It can be obtained by forming a layer of a charge generating substance or by forming a layer formed by binding the charge generating substance on a layer serving as a base using a binder resin. As a method for forming the charge generation layer using a binder resin, various methods such as a known method can be used, and usually, for example, a coating liquid in which a charge generation material is dispersed or dissolved in a suitable solvent together with a binder resin. Is applied onto a predetermined base layer and dried. The thickness of the charge generation layer thus obtained is 0.01 to 2.
0 microns, preferably 0.1-0.8 microns. When the thickness of the charge generation layer is less than 0.01 μm, it is difficult to form a layer with a uniform thickness, and
If it exceeds 2.0 microns, the electrophotographic characteristics may be deteriorated.

As the charge generating substance used here, various compounds known in, for example, JP-A-8-225639 can be used. Specific compounds include
Selenium alone such as amorphous selenium and trigonal selenium, tellurium alone, selenium alloys such as selenium-tellurium alloys, selenium-arsenic alloys, selenium compounds or selenium-containing compositions such as As ₂ Se ₃ , zinc oxide, cadmium sulfide, Alloys such as antimony sulfide, zinc sulfide, CdS-Se, inorganic materials composed of Group 12 and Group 16 elements, oxide semiconductors such as titanium oxide, silicon-based materials such as amorphous silicon, τ-type non-metallic phthalocyanine, χ Metal-free phthalocyanine pigments such as type-free metal phthalocyanine, α-type copper phthalocyanine, β-type copper phthalocyanine, γ-type copper phthalocyanine, ε-type copper phthalocyanine, X-type copper phthalocyanine, A-type titanyl phthalocyanine, B-type titanyl phthalocyanine, C-type titanyl phthalocyanine , D-type titanyl phthalocyanine, E-type Oxyphthalocyanine, F type titanyl phthalocyanine, G type titanyl phthalocyanine,
H-type titanyl phthalocyanine, K-type titanyl phthalocyanine, L-type titanyl phthalocyanine, M-type titanyl phthalocyanine, N-type titanyl phthalocyanine, Y-type titanyl phthalocyanine, oxo titanyl phthalocyanine, X
Metal phthalocyanine pigments such as titanyl phthalocyanine showing a strong diffraction peak at a black angle 2θ of 27.3 ± 0.2 degrees in a line diffraction diagram, cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, Indigo pigment, perylene pigment, pyrylium dye, squarium pigment, anthantrone pigment, benzimidazole pigment, azo pigment, thioindigo pigment, quinoline pigment, lake pigment, oxazine pigment, dioxazine pigment, triphenylmethane pigment, azulhenium dye, triarylmethane Dyes, xanthine dyes, thiazine dyes, thiapyrylium dyes, polyvinyl carbazole, bisbenzimidazole pigments and the like can be mentioned.

Among these compounds, as the dyes and pigments, the compounds specifically exemplified in the above-mentioned JP-A-8-225639 are particularly preferably used. These compounds can be used alone or as a mixture of two or more kinds as a charge generating substance. The binder resin used for the charge generation layer is not particularly limited, and various known resins can be used. Specifically, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, epoxy resin, phenol resin, polyamide, polyketone, Polyacrylamide, butyral resin, polyester resin, vinylidene chloride-vinyl chloride copolymer, methacrylic resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone Resin, silicone-alkyd resin, phenol-
Formaldehyde resin, styrene-alkyd resin, melamine resin, polyether resin, benzoguanamine resin, epoxy acrylate resin, urethane acrylate resin, poly-N-vinyl carbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, Nitrocellulose, carboxy-methylcellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyltoluene-styrene copolymer, soybean oil-modified alkyd resin, nitrated polystyrene, polymethylstyrene, polyisoprene, polythiocarbonate, poly Arylate, polyhaloarylate, polyallyl ether, polyvinyl acrylate, polyester acrylate And the like. As the binder resin in the charge generation layer, the above-mentioned polycarbonate resin can also be used.

Next, as for the charge transport layer of the electrophotographic photoreceptor of the present invention, it is only necessary to form a layer containing the above polycarbonate resin on a layer serving as a base, for example, a charge generation layer. As a method for forming the charge transport layer, various known methods can be used. A coating solution obtained by dispersing or dissolving the above-described polycarbonate resin and a charge transport substance in an appropriate solvent is applied to a predetermined base. It can be performed by a method of applying on a layer to be formed and drying.

Here, the compounding ratio of the charge transporting substance and the polycarbonate resin is preferably 0.1: 9 by weight.
9.9 to 70:30, more preferably 1:99 to 6
0:40. Then, the compounding ratio of the charge transporting material may be increased in accordance with the content ratio of the resin component used in combination. When the compounding ratio is less than 0.1, the charge transporting performance decreases, and when it exceeds 70, the printing durability decreases.

The thickness of the thus formed charge transporting layer is 5 to 100 microns, preferably 10 to 30 microns. If the thickness is less than 5 microns, the initial potential will be reduced, and if it exceeds 100 microns, the electrophotographic properties may be reduced. The compound which can be used as the charge transport material is described in
There are various compounds known in, for example, JP-A-225639. Such compounds include carbazole compounds, indole compounds, imidazole compounds, oxazole compounds, pyrazole compounds, oxadiazole compounds, pyrazoline compounds, thiadiazole compounds, aniline compounds, hydrazone compounds, aromatic amine compounds, aliphatic amine compounds, stilbene Compound, fluorenone compound, butadiene compound, quinone compound, quinodimethane compound, thiazole compound, triazole compound, imidazolone compound, imidazolidine compound, bisimidazolidine compound, oxazolone compound, benzothiazole compound, benzimidazole compound, quinazoline compound, benzofuran compound, acridine Compound, phenazine compound, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthra Emissions, polyvinyl acridine, poly-9-vinylphenyl anthracene, pyrene -
A formaldehyde resin, an ethyl carbazole resin, or a polymer having these structures in the main chain or side chain is suitably used. Of these compounds, the compounds disclosed in
Compounds specifically exemplified in JP-A-225639 are particularly preferably used. These compounds are:
Species may be used alone or in combination of two or more.

In the electrophotographic photoreceptor of the present invention, an undercoat layer, which is generally used, can be provided between the conductive substrate and the photosensitive layer. As this undercoat layer,
Fine particles of titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, silicon oxide, polyamide resin, phenolic resin, casein, Components such as melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol and polyvinyl butyral resin can be used. As the resin used for the undercoat layer, the binder resin described above or the polycarbonate resin of the present invention may be used. These fine particles and resins can be used alone or in various mixtures. When used as a mixture of these, it is preferable to use inorganic fine particles and a resin in combination, since a film with good smoothness is formed.

The thickness of the undercoat layer is 0.01 to 10 μm, preferably 0.01 to 1 μm. If the thickness is less than 0.01 μm, it is difficult to form the undercoat layer uniformly, and if it exceeds 10 μm, the electrophotographic properties may be degraded. In addition, a known blocking layer, which is generally used, can be provided between the conductive substrate and the photosensitive layer. As this blocking layer, a resin of the same type as the binder resin described above can be used. Further, the polycarbonate resin of the present invention may be used. The thickness of this blocking layer is
It is between 0.01 and 20 microns, preferably between 0.1 and 10 microns. If the thickness is less than 0.01 μm, it is difficult to form the blocking layer uniformly, and if it exceeds 20 μm, the electrophotographic properties may deteriorate.

Further, in the electrophotographic photosensitive member of the present invention, a protective layer may be laminated on the photosensitive layer. For this protective layer, the same kind of resin as the binder resin described above can be used. It is particularly preferable to use the polycarbonate resin of the present invention. The thickness of this protective layer is 0.01 to
It is 20 microns, preferably 0.1 to 10 microns. The protective layer contains the charge generating substance, the charge transporting substance, an additive, and a conductive material such as a metal and its oxide, nitride, salt, alloy, carbon black, and organic conductive compound. Is also good.

Further, in order to improve the performance of the electrophotographic photoreceptor, a binder, a plasticizer, a curing catalyst, a fluidity-imparting agent, a pinhole controlling agent, a spectral sensitivity increasing A sensitizer (sensitizing dye) may be added. Additives such as various chemical substances, antioxidants, surfactants, anti-curl agents, and leveling agents are used to prevent increase in residual potential, decrease in charge potential, and decrease in sensitivity to repeated use. Can be added.

As the binder, silicone resin, polyamide resin, polyurethane resin, polyester resin,
Epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, polyisobrene resin, melamine resin, benzoguanamine resin, polychloroprene resin, polyacrylonitrile resin, ethylcellulose resin, nitrocellulose resin, urea resin, Phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate /
Examples thereof include a vinyl chloride copolymer resin and a polyester carbonate resin. Also, heat and / or light curable resins can be used. In any case, there is no particular limitation as long as the resin is electrically insulating and can form a film in a normal state.

This binder is preferably added at a blending ratio of 1 to 200% by weight, more preferably 10 to 100% by weight, based on the polycarbonate resin. If the blending ratio of the binder is less than 1% by weight, the film of the photosensitive layer tends to be non-uniform, and the image quality tends to be inferior.
If it exceeds, the sensitivity tends to decrease and the residual potential tends to increase.

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

Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalenedisulfonic acid. Examples of the fluidity-imparting agent include Modaflow and Acronal 4F.
Examples of the pinhole control agent include benzoin and dimethyl phthalate. These plasticizers, curing catalysts, fluidity-imparting agents, and pinhole controlling agents are preferably used in an amount of 5% by weight or less based on the charge transport material.

When a sensitizing dye is used as the spectral sensitivity sensitizer, for example, triphenylmethane dyes such as methyl violet, crystal violet, night blue and Victoria blue, erythrosine, rhodamine B, rhodamine 3R, Suitable are acridine dyes such as acridine orange and flapeosin, thiazine dyes such as methylene blue and methylene green, oxazine dyes such as capri blue and meldra blue, cyanine dyes, merocyanine dyes, styryl dyes, pyrylium salt dyes, and thiopyrium salt dyes. .

An electron-accepting substance can be added to the photosensitive layer for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Specific examples thereof include succinic anhydride, maleic anhydride, dibromomaleic anhydride,
Phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, melitic anhydride,
Tetracyanoethylene, tetracyanoquinodimethane, o
-Dinitrobenzene, m-dinitrobenzene, 1,3
5-trinitrobenzene, p-nitrobenzonitrile,
Picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4 '-Dinitrobenzophenone, 4-nitrobenzalmalone dinitrile,
ethyl α-cyano-β- (p-cyanophenyl) acrylate, 9-anthracenylmethylmalondinitrile, 1
-Cyano- (p-nitrophenyl) -2- (p-chlorophenyl) ethylene, 2,7-dinitrofluorenone,
2,4,7-trinitrofluorenone, 2,4,5,7
-Tetranitrofluorenone, 9-fluorenylidene-
(Dicyanomethylene malononitrile), polynitro-9
-Fluorenylidene- (dicyanomethylenemalonodinitrile), picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid Compounds having a high electron affinity, such as phthalic acid, phthalic acid and melitic acid are preferred. These compounds may be added to any of the charge generation layer and the charge transport layer, and the compounding ratio is 0.01 to 20 with respect to the charge generation substance or the charge transport substance.
0% by weight, preferably 0.1 to 50% by weight.

In order to improve surface properties, ethylene tetrafluoride resin, ethylene trifluoride chloride resin, ethylene tetrafluoride hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, dichloride difluoride Ethylene resins, their copolymers, and fluorine-based graft polymers may be used. The mixing ratio of these surface modifiers is 0.1 to 60% by weight, preferably 5 to 4% by weight, based on the binder resin.
0% by weight. If the content is less than 0.1% by weight, surface modification such as surface durability and surface energy reduction is not sufficient, and if it is more than 60% by weight, electrophotographic properties may be deteriorated.

The antioxidants include hindered phenol antioxidants, aromatic amine antioxidants, hindered amine antioxidants, sulfide antioxidants,
Organic phosphoric acid antioxidants are preferred. Among these antioxidants, compounds specifically exemplified in the above-mentioned JP-A-8-225639 can be particularly preferably used. The mixing ratio of these antioxidants is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the charge transporting substance.

These antioxidants may be used alone or as a mixture of two or more. Further, these may be used in addition to the photosensitive layer, in addition to the surface protective layer, the undercoat layer, and the blocking layer. The charge generation layer, the solvent used when forming the charge transport layer,
For example, aromatic solvents such as benzene, toluene, xylene, chlorobenzene and anisole; ketones such as acetone, methyl ethyl ketone and cyclohexanone; alcohols such as methanol, ethanol and isopropanol; esters such as ethyl acetate and ethyl cellosolve; Examples include halogenated hydrocarbons such as carbon chloride, chloroform, dichloromethane, and tetrachloroethane; ethers such as tetrahydrofuran and dioxane; dimethylformamide, dimethylsulfoxide, and diethylformamide. These solvents may be used alone or as a mixture of two or more.

Next, as a method for forming the charge transport layer, a coating solution prepared by dispersing or dissolving the charge transport material, additives, and a polycarbonate resin used as a binder resin in a solvent is prepared. Is applied on, for example, the charge generation layer serving as a base for forming a charge transport layer in a form in which the polycarbonate resin coexists with a charge transport material as a binder resin.

As a method of preparing the coating liquid, the above-mentioned prepared raw material can be dispersed or dissolved by using a ball mill, an ultrasonic wave, a paint shaker, a red devil, a sand mill, a mixer, an attritor, or the like. The method of applying the coating liquid obtained in this manner includes dip coating, electrostatic coating, powder coating, spray coating, roll coating, applicator coating, spray coater coating, and bar coating. Coater coating method, roll coater coating method, dip coater coating method, doctor blade coating method, wire bar coating method, knife coater coating method, attritor coating method, spinner coating method, bead coating method, blade coating method, curtain coating method, etc. Can be adopted.

The photosensitive layer of the single-layer type electrophotographic photosensitive member is
The polycarbonate resin, a charge generating substance, an additive,
It is formed by using a charge transporting material or another binder resin if desired. In this case, the preparation of the coating liquid, the coating method, the formulation of the additives, and the like are the same as those in the formation of the photosensitive layer in the laminated electrophotographic photosensitive member. Further, in this single-layer type electrophotographic photoreceptor, an undercoat layer, a blocking layer, and a surface protective layer may be provided in the same manner as described above. When forming these layers, it is preferable to use the polycarbonate resin.

The thickness of the photosensitive layer in the single-layer type electrophotographic photoreceptor is 5 to 100 μm, preferably 8 to 50 μm. If the thickness is less than 5 μm, the initial potential tends to be low, and exceeds 100 μm. And the electrophotographic characteristics may be reduced. The ratio of the charge generating substance to the binder resin used in the production of this single-layer type electrophotographic photoreceptor is 1:99 to 30:70, preferably 3: 9 by weight.
7 to 15:85. In addition, the ratio of the charge transporting material to the polycarbonate resin is 5:95 to 70: 3 by weight.
0, preferably 10:90 to 60:40.

The electrophotographic photoreceptor of the present invention thus obtained is a photoreceptor having excellent abrasion resistance and maintaining excellent printing durability and electrophotographic properties over a long period of time. It is suitably used in various electrophotographic fields such as monochrome, multi-color, full-color; analog, digital) printers (laser, LED, liquid crystal shutter), facsimile, plate making machine and the like.

In using the electrophotographic photosensitive member of the present invention, for charging, corona discharge (corotron, scorotron), contact charging (charging roll, charging brush) and the like are used. For the exposure, halogen lamps, fluorescent lamps, lasers (semiconductors, He-Ne), LEDs,
Any of the photoconductor internal exposure methods may be employed. For development, a dry development method such as a cascade development, a two-component magnetic brush development, a one-component insulating toner development, a one-component conductive toner development, or a wet development method using a liquid toner is used. For the transfer, an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method is used. For fixing, heat roller fixing, radiant flash fixing, open fixing, pressure fixing and the like are used. Further, a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, and the like are used for cleaning and static elimination.

[0067]

The present invention will be described more specifically with reference to the following examples. [Example 1] 2,2-bis (4-hydroxyphenyl)
To a solution of 74 g of propane dissolved in 550 ml of a 6% by weight aqueous sodium hydroxide solution, 250 ml of methylene chloride was added, and the mixture was stirred and cooled.
Phosgene gas was blown into the solution at a rate of 950 ml / min for 15 minutes. Then, the reaction solution was allowed to stand and separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 4 in an organic phase and having a chloroformate group at a molecular end.

To a methylene chloride solution of this polycarbonate oligomer, methylene chloride was added to make a total amount of 450 ml. Then, 20 g of a dihydroxyimine compound having the following chemical structure was added to 150 ml of a 2 N aqueous potassium hydroxide solution. The dissolved solution and 1.0 g of p-tert-butylphenol as a molecular weight regulator were added.

[0069]

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Next, while vigorously stirring the mixture, 2 ml of a 7% by weight aqueous solution of triethylamine was added as a catalyst, and the mixture was stirred at 25 ° C. for 1 hour.
The reaction was performed for 5 hours. After completion of the reaction, the reaction product was diluted with 1 liter of methylene chloride, then twice with 1.5 liter of water, once with 1 liter of hydrochloric acid of 0.01N concentration, and twice with 1 liter of water. After washing, the organic layer was put into methanol and purified by reprecipitation to obtain a polycarbonate resin.

The reduced viscosity [ηsp / c] of the polycarbonate resin obtained above was measured at 20 ° C. (measured under the same conditions in the following Examples) of a solution having a concentration of 0.5 g / deciliter using methylene chloride as a solvent. Is 0.50
It was deciliter / g. To measure this reduced viscosity,
Using an automatic viscosity measurement device VMR-042 manufactured by Rigo Co., Ltd., the viscosity was measured by an automatic viscosity Ubbelohde improved viscometer (RM type). In the ¹ H-NMR spectrum measured for this polycarbonate resin, an absorption peak based on methyl of an isopropylidene group was observed at 1.7 ppm, and an absorption peak based on an aromatic ring of imine was observed at 7.8 to 10 ppm. . From these intensity ratios, [a-1] copolymerization of a repeating unit derived from the dihydroxyimine compound and [b-1] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane As a result of calculating the composition, [a-1]: [b-1] = 0.
20: 0.80. Therefore, it was recognized that the chemical structure of the polycarbonate resin obtained here was as follows.

[0072]

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Example 2 A polycarbonate resin was obtained in the same manner as in Example 1 except that 22 g of a dihydroxyimine compound having the following chemical structure was used instead of the dihydroxyimine compound used in Example 1. .

[0074]

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The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.45 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum, an absorption peak based on the methyl group of the isopropylidene group was recognized at 1.7 ppm, and an absorption peak based on the aromatic ring of imine was recognized at 7.8 to 10 ppm. As a result of calculating the copolymer composition of this polycarbonate resin from these strength ratios, [a-2] a repeating unit derived from the dihydroxyimine compound and [b-1] 2,2-bis (4-hydroxyphenyl) The repeating unit derived from propane is [a-2]: [b-1] = 0.20: 0.8
It was 0. Therefore, it was recognized that the chemical structure of the polycarbonate resin obtained here was as follows.

[0076]

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Example 3 In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 2,
Using 54 g of 2-bis (3-methyl-4-hydroxyphenyl) propane, as a dihydroxyimine compound,
Dihydroxyimine compound 91 having the following chemical structure:
A polycarbonate resin was obtained in the same manner as in Example 1 except that g was used.

[0078]

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The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.40 deciliter / g. Further, as a result of measuring the ¹ H-NMR spectrum, an absorption peak based on the methyl group of the isopropylidene group was found at 1.7 ppm, and an absorption peak based on the aromatic ring of imine was found at 7.8 to 10 ppm. As a result of calculating the copolymer composition of this polycarbonate resin from these strength ratios, [a-3] a repeating unit derived from the dihydroxyimine compound and [b-2] 2,2-bis (3-
And a repeating unit derived from (methyl-4-hydroxyphenyl) propane is [a-3]: [b-2] = 0.50:
0.50. Therefore, it was recognized that the chemical structure of the polycarbonate resin obtained here was as follows.

[0080]

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Example 4 Instead of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 2,
A polycarbonate resin was prepared in the same manner as in Example 1 except that 71 g of 2-bis (3-phenyl-4-hydroxyphenyl) propane was used and 52 g of a dihydroxyimine compound having the following chemical structure was used as the dihydroxyimine compound. Obtained.

[0082]

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The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.35 deciliter / g. As a result of measuring the ¹ H-NMR spectrum, an absorption peak based on the methyl group of the isopropylidene group was found at 1.7 ppm, and an absorption peak based on the aromatic ring of the imide was found at 7.8 to 10 ppm. As a result of calculating the copolymer composition of this polycarbonate resin from these strength ratios, [a-4] a repeating unit derived from the dihydroxyimine compound and [b-3] 2,2-bis (3-
A repeating unit derived from (phenyl-4-hydroxyphenyl) propane is [a-4]: [b-3] = 0.5
0: 0.50. Therefore, it was recognized that the chemical structure of the polycarbonate resin obtained here was as follows.

[0084]

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Example 5 An electrophotographic photosensitive member was used in which a polyethylene terephthalate resin film on which aluminum metal was vapor-deposited was used as a conductive substrate, and a charge-generating layer and a charge-transporting layer were sequentially laminated on the surface to form a laminated photosensitive layer. Body manufactured. 0.5 parts by weight of oxotitanium phthalocyanine was used as the charge generating substance, and 0.5 parts by weight of butyral resin was used as the binder resin. These were added to 19 parts by weight of methylene chloride as a solvent, and dispersed by a ball mill.
The dispersion is applied to the surface of the conductive substrate film by a bar coater and dried to obtain a film having a thickness of about 0.1.
A 5 μm charge generation layer was formed.

Next, 0.5 g of the polycarbonate resin obtained in Example 1 and 0.5 g of a compound having the following chemical structure were used as materials for forming the charge transport layer, and these were dissolved in 10 ml of tetrahydrofuran as a solvent. This was made a coating liquid.

[0087]

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Next, this coating solution was applied on the above-mentioned charge generating layer by an applicator and dried to form a charge transporting layer having a thickness of about 20 μm. The obtained electrophotographic photoreceptor is charged with an electrostatic charging tester EPA-810.
The electrophotographic characteristics were measured using No. 0 (manufactured by Kawaguchi Electric Manufacturing Co., Ltd.). The conditions for the measurement were corona discharge at -6 kv, and the initial surface potential at that time, the residual potential 5 seconds after the light irradiation at 10 lux, and the half-life exposure amount (E _1/2 ) were measured. Table 1 shows the measurement results. Further, in order to evaluate the durability of the electrophotographic photosensitive member, a wear resistance test of the photosensitive layer was performed. As a test device, a Suga abrasion tester NUS-ISO-3 type (manufactured by Suga Test Machine Co., Ltd.) was used, and as a condition for the abrasion test, a worn paper with a load of 500 g (containing alumina particles having a particle size of 3 μm) Was brought into contact with the surface of the photosensitive layer and reciprocated 2000 times to measure the amount of weight loss. Table 1 shows the results.

Example 6 As a material for forming a charge transport layer, 0.5 g of the polycarbonate resin obtained in Example 2 and 0.5 g of a charge transport material having the following chemical structure were used.

[0090]

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An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 5 except for the above. Table 1 shows the evaluation results.

Example 7 As a material for forming the charge transport layer, 0.5 g of the polycarbonate resin obtained in Example 2 and 0.5 g of a charge transport material having the following chemical structure were used.

[0093]

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Except for the above, an electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 5. Table 1 shows the evaluation results.

Example 8 As a material for forming a charge transport layer, 0.5 g of the polycarbonate resin obtained in Example 3 and 0.5 g of a charge transport material having the following chemical structure were used.

[0096]

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An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 5 except for the above. Table 1 shows the evaluation results.

Comparative Example 1 As a material for forming the charge transport layer, a polycarbonate resin using 1,1-bis (4-hydroxyphenyl) cyclohexane as a raw material (reduced viscosity;
An electrophotographic photoreceptor was manufactured and evaluated in the same manner as in Example 5, except that 0.5 g of (0.77 deciliter / g) and 0.5 g of the charge transport material used in Example 5 were used. Table 1 shows the evaluation results.

Comparative Example 2 As a material for forming the charge transport layer, a polycarbonate resin using 2,2-bis (4-hydroxyphenyl) propane as a raw material (reduced viscosity: 0.5
An electrophotographic photoreceptor was manufactured and evaluated in the same manner as in Example 5, except that 0.5 g (6 deciliters / g) and 0.5 g of the charge transport material used in Example 5 were used. Table 1 shows the evaluation results.

[0100]

[Table 1]

[0101]

The polycarbonate resin of the present invention is excellent in optical properties, electrical properties, mechanical properties, and especially abrasion resistance. Further, since the electrophotographic photoreceptor of the present invention uses a wear-resistant polycarbonate resin having a specific chemical structure as a binder resin for the photosensitive layer, the abrasion resistance of the surface of the photosensitive layer is improved. A product with excellent properties is obtained.

Claims (4)

[Claims] 1. A repeating unit represented by the following general formula [1]:
Repeating unit represented by position (1) and general formula [2]
(2) is the sum of repeating unit (1) and repeating unit (2)
The molar ratio of the repeating unit (1) to [(1) / ((1)
+ (2))] is 0.001 to 1
Recarbonate resin. Embedded image[R in the formula [1]¹, R^TwoIs a hydrogen atom, having 1 to 1 carbon atoms
An alkyl group optionally having 2 substituents, having 6 to 6 carbon atoms
18 aryl groups or fused polycyclic carbons having 6 to 18 carbon atoms
Represents a hydride group, s represents an integer of 0 to 4, and Y represents the following
General formula [3] or [4],(R in formula [3]^ThreeIs a halogen atom having 1 to 12 carbon atoms
Having an alkoxy group having 1 to 12 carbon atoms
An alkyl group, an aryl group having 6 to 18 carbon atoms or
A condensed polycyclic hydrocarbon group having 6 to 18 carbon atoms;
Or 2 and R in formula [4]^FourR^FiveAre each independently
Hydrogen atom, alkyl group having 1 to 12 carbon atoms, trifluoro
A methyl group or an aryl group having 6 to 18 carbon atoms;
Is an integer of 0 to 4, b is an integer of 1 to 12)
Ar in the formula [2] represents the following general formula [5a]
~ [5d], embedded image(X in the formula [5a] is a single bond, -O-, -CO-,-
S-, -SO-, -SO _Two-, -CR⁸R⁹-(Just
Then R⁸, R⁹Are each independently a hydrogen atom, having 1 to 12 carbon atoms
Alkyl or trifluoromethyl group of
Substituted or unsubstituted cycloalkylide having 6 to 12 prime numbers
, A substituted or unsubstituted α, ω- having 2 to 12 carbon atoms
Alkylene group, 9,9-fluorenylidene group, 1,8-
Menthandiyl group, 2,8-menthandiiyl group, substituted
Or an unsubstituted pyradylidene group or a group having 6 to 24 carbon atoms
A substituted or unsubstituted arylene group represented by the formula [5a]
R in ~ [5d]⁶, R⁷Are each independently a hydrogen atom,
Alkyl group of 1 to 12 primes, trifluoromethyl group, charcoal
An alkoxy group having 1 to 12 carbon atoms and a substituent having 1 to 12 carbon atoms
Alkyl group optionally having 6 to 18 carbon atoms
Or an unsubstituted aryl group or a group having 6 to 12 carbon atoms
A substituted or unsubstituted aryloxy group, m represents
Independently, an integer of 0 to 4, q is an integer of 0 to 6, n is 0 to 20
An integer of 0 and p each independently represent an integer of 0 to 6)
Represents a group represented by 2. 0.5 g / methylene chloride as a solvent.
2. The polycarbonate resin according to claim 1, wherein the reduced viscosity [η _SP / c] measured at a concentration of deciliter and a temperature of 20 ° C. is at least 0.1 deciliter / g. 3. A reaction of the dihydroxyimine compound represented by the following general formula [6] alone or the dihydroxyimine compound and a dihydroxy compound represented by the following general formula [7] with a carbonate-forming compound: The method for producing a polycarbonate resin according to claim 1 or 2, wherein: Embedded image [R ¹ in the formula (6), R ^2, Y, s have the same meaning as R ^1, R ^2, Y, s of the formula [1] in, Ar in formula (7) is Has the same meaning as Ar in the formula [2]] 4. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the polycarbonate resin according to claim 1.