JPH11172003A - Method for producing crosslinked polycarbonate resin, crosslinked polycarbonate resin, and electrophotographic photoreceptor - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To produce a crosslinked polycarbonate resin having high utility in fields such as electric / electronic equipment and optical equipment,
In the cross-linking step, a method for producing a cross-linked polycarbonate resin capable of performing effective cross-linking without deteriorating the performance of the polycarbonate resin and obtaining a molded article particularly excellent in abrasion resistance, and the cross-linking obtained by the manufacturing method Provided are a polycarbonate resin and an electrophotographic photoreceptor having excellent durability using the crosslinked polycarbonate resin. SOLUTION: A method for producing a crosslinked polycarbonate resin in which a polycarbonate resin having a carbon-carbon unsaturated bond is hydrosilylated with a silicon compound having two or more silicon-hydrogen bonds in a molecule, and a crosslinkable resin obtained by the method An electrophotographic photoreceptor comprising a photosensitive substrate containing a polycarbonate resin and a crosslinked polycarbonate resin on a conductive substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a crosslinked polycarbonate resin having excellent mechanical properties, optical properties and electrophotographic properties, and a crosslinked polycarbonate resin produced by the method. The present invention also relates to a highly durable electrophotographic photosensitive member containing the crosslinked polycarbonate resin as a binder resin in a photosensitive layer.

[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, since operations such as corona charging, toner development, transfer to paper, and cleaning are repeatedly performed on the surface of the photosensitive layer, an electric or mechanical external force is applied each time these operations are performed. Added. 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, conventionally,
As the polycarbonate resin, 2,2-bis (4-
Hydroxyphenyl) propane and 2,2-bis (4-
Although materials using hydroxyphenyl) cyclohexane as a raw material have been used, they have not been sufficiently satisfactory in terms of durability. For this reason, for example, Japanese Patent Application Laid-Open No. 4-29
No. 1348 discloses an electrophotographic method in which a crosslinkable polycarbonate resin having a carbon-carbon unsaturated bond is used as a binder resin, a photosensitive layer containing the same is applied to a conductive substrate, and then the crosslinkable polycarbonate resin is crosslinked. The body has been proposed. By the way, in this case, since a crosslinking reaction is performed by adding a radical initiator to the crosslinkable polycarbonate resin, the radicals generated here may cause a molecular chain of the polycarbonate resin to be cut or yellowed due to a chemical change. There is a problem that there is. There is also a problem that the charge transport material contained in the binder resin undergoes a chemical change due to the radicals generated here, thereby lowering its performance. Therefore, the performance and durability of the electrophotographic photoreceptor have been reduced due to the molecular cleavage or chemical change, so that they have not been sufficiently satisfactory.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and is intended to provide a crosslinked polycarbonate capable of obtaining a molded article having excellent optical properties, mechanical properties, and especially abrasion resistance. An object of the present invention is to provide a resin and a method for producing the resin. It is another object of the present invention to provide an electrophotographic photoreceptor having excellent durability using the crosslinked polycarbonate resin as a binder resin for an organic electrophotographic photoreceptor.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a polycarbonate resin having a carbon-carbon unsaturated bond has two carbon atoms per molecule.
It has been found that a crosslinked polycarbonate resin obtained by reacting a silicon compound having one or more silicon-hydrogen bonds and hydrosilylating is excellent in optical properties, mechanical properties, and especially abrasion resistance. Furthermore, they have found that when this crosslinked polycarbonate resin is used as a binder resin for an organic electrophotographic photosensitive member, an electrophotographic photosensitive member having excellent durability can be obtained, and the present invention has been completed based on these findings.

That is, the gist of the present invention is as follows. (1) A polycarbonate resin having a carbon-carbon unsaturated bond is converted into silicon-hydrogen in the same molecule in the presence of one or more substances selected from a transition metal catalyst, a base catalyst and a radical chemical species. A method for producing a crosslinked polycarbonate resin, comprising reacting with a silicon compound having two or more bonds for hydrosilylation. (2) The above-mentioned polycarbonate resin having a carbon-carbon unsaturated bond comprises a repeating unit (1) represented by the following general formula [1] or a repeating unit (1) represented by the following general formula [1] and Repeating unit (2) represented by formula [2]
The method for producing a crosslinked polycarbonate resin according to the above (1), which is a polycarbonate resin having the following.

[0009]

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[In the formula [1], Ar ¹ is

[0011]

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(X ¹ in the formula [1a] is a single bond, -O
-, - CO -, - S -, - SO -, - SO 2 -, - CR
³ R ⁴ — (where R ³ and R ⁴ each independently represent a hydrogen atom,
An alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms, 12 substituted or unsubstituted α, ω-alkylene groups, 9,9-fluorenylidene group, 1,8-menthanediyl group, 2,8-menthanediyl group, substituted or unsubstituted pyradylidene group, 6 carbon atoms
To 12 substituted or unsubstituted arylene groups or the following general formula [3],

[0013]

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(R ⁵ in the formula [3] is each independently a hydrogen atom, a halogen atom, a trifluoromethyl group,
A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms; Which is an integer of)
A in the formula [1a] - [1c] _{is, - (CH 2) h -} , -
_{O- (CH 2) h -,} - CO- (CH 2) h -, - CO
O- (CH ₂ ) _h — (where h is an integer of 0 to 6), FG is an ethynyl group or a vinyl group, p ¹ and p ² are integers of 0 to 4 (However, p ¹ + p
² is an integer of 1 to 8), q is 1 or 2, s is an integer of 1 to 6, and Y in the formula [1d] has at least one carbon-carbon unsaturated bond. 2 to 1 carbon atoms
A cycloalkylidene group having 5 to 12 carbon atoms and having a chain or cyclic hydrocarbon group of 2 as a substituent;
R ¹ in a] ~ [1g] is a hydrogen atom, a halogen atom,
A trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, and R ² is the same group as R ¹ However, R ² may be bonded to each other by a hydrocarbon group having 1 to 10 carbon atoms, c in the formula [1e] is 0 or 1, and e in the formula [1f] [1g] is 1 to 200 is an integer, and the sum of d + e is an integer of 1 to 200, r is each independently an integer of 0 to 4, t is each independently an integer of 0 to 6, and g is 0 to 200. Is an integer of
Which is a divalent group represented by the general formula [2]
² is

[0015]

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(X ² , R ⁶ in the formulas [2a] to [2d],
r, t, and g have the same meanings as X ¹ , R ¹ , r, t, and g, and k is an integer of 0 to 6. (3) The crosslink according to the above (1) or (2), wherein the silicon compound having two or more silicon-hydrogen bonds in the same molecule is represented by the following general formulas [4a] to [4f]. Method for producing polycarbonate.

[0017]

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[In the formulas [4a] to [4f], R ⁷ has the same meaning as R ¹ , i is an integer of 0 to 200,
n is an integer of 2 to 100, n + m is an integer of 2 to 200, u + v is an integer of 0 to 200, and w is 0 to 6
Is an integer. (4) The transition metal catalyst is an iron catalyst, a ruthenium catalyst,
The method for producing a crosslinked polycarbonate according to any one of the above (1) to (3), which is one or more catalysts selected from a cobalt catalyst, a rhodium catalyst, an iridium catalyst, a nickel catalyst, a palladium catalyst, and a platinum catalyst. . (5) A polycarbonate resin having a carbon-carbon unsaturated bond is converted into silicon-hydrogen in the same molecule in the presence of one or more substances selected from transition metal catalysts, base catalysts and radical chemical species. A crosslinked polycarbonate resin obtained by reacting a silicon compound having two or more bonds to form a hydrosilylation reaction. (6) An electrophotographic photosensitive member having at least a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the crosslinked polycarbonate resin described in (5) above.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The crosslinked polycarbonate resin of the present invention is produced by reacting a polycarbonate resin having a carbon-carbon unsaturated bond with a silicon compound having two or more silicon-hydrogen bonds in the same molecule. Can be. The polycarbonate resin having a carbon-carbon unsaturated bond used herein may be any one having a carbon-carbon unsaturated bond in its main chain, side chain or terminal as a repeating unit constituting the polycarbonate resin. It may be a union or a copolymer. The polymer chain may have any of a linear, branched, or cyclic structure, and further has a special terminal structure or special structure by using a terminal stopper or a branching agent during synthesis. A branching structure may be introduced.

As for the method of producing such a polycarbonate resin having a carbon-carbon unsaturated bond, for example, phosgene or the like is used as a carbonate-forming compound, and a carbon-carbon unsaturated bond is formed in the presence of a suitable acid binder. A method of reacting a dihydric phenol having a saturated bond alone or a method of reacting a dihydric phenol having a carbon-carbon unsaturated bond with a dihydric phenol having no carbon-carbon unsaturated bond, or as a carbonate-forming compound. A transesterification method using bisaryl carbonate may be employed. The dihydric phenol having a carbon-carbon unsaturated bond may be used alone or in combination of two or more.
As for the dihydric phenol having no carbon-carbon unsaturated bond, one kind may be used alone, or two or more kinds may be used in combination. These reactions are carried out in the presence of a terminal terminator and / or a branching agent as required.

The dihydric phenol having a carbon-carbon unsaturated bond includes 4,4'-dihydroxy-3,3'-
Divinyl biphenyl, 4,4'-dihydroxy-3,
3'-diallylbiphenyl, 3,3 ', 5,5'-tetraallyl-4,4'-dihydroxybiphenyl, bis (3-vinyl-4-hydroxyphenyl) methane, bis (3-allyl-4-hydroxyphenyl) Methane, bis (3-allyl-4-hydroxyphenyl) diphenylmethane, 1,1-bis (3-vinyl-4-hydroxyphenyl) ethane, 1,1-bis (3-allyl-4-hydroxyphenyl) ethane, 1, , 1-bis (3-allyl-4
-Hydroxyphenyl) -1-phenylethane, 2,2
-Bis (3-vinyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-vinyl-4-hydroxy-5-methylphenyl) Propane, 2,2-bis (3-allyl-4-hydroxy-5-methylphenyl)
Propane, 2,2-bis (3-allyl-4-hydroxy-5-phenylphenyl) propane, 2,2-bis [3
-(3-butenyl) -4-hydroxyphenyl] propane, 2,2-bis [3- (4-pentenyl) -4-hydroxyphenyl] propane, 2,2-bis [3- (5-
Hexenyl) -4-hydroxyphenyl] propane, 2
-(4-hydroxyphenyl) -2- (3-allyl-4
-Hydroxyphenyl) propane, 2,2-bis (3,
5-diallyl-4-hydroxyphenyl) propane,
2,2-bis (3-vinyl-4-hydroxyphenyl)
Butane, 2,2-bis (3-allyl-4-hydroxyphenyl) butane, 3,3-bis (3-vinyl-4-hydroxyphenyl) pentane, 3,3-bis (3-allyl-4-hydroxyphenyl) ) Pentane, 1,1-bis (3-vinyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, bis (3-vinyl-4-hydroxyphenyl) ether, Bis (3-allyl-4-hydroxyphenyl) ether, bis (3-vinyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl)
Hydroxyphenyl) sulfide, bis (3-vinyl-
4-hydroxyphenyl) sulfoxide, bis (3-allyl-4-hydroxyphenyl) sulfoxide, bis (3-vinyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone,
3,3′-divinyl-4,4′-dihydroxybenzophenone, 3,3′-diallyl-4,4′-dihydroxybenzophenone, 4,4′-dihydroxybenzalacetophenone, 9,9-bis (3-vinyl- 4-hydroxyphenyl) fluorene, 9,9-bis (3-allyl-
4-hydroxyphenyl) fluorene, 9,9-bis (3-allyl-4-hydroxy-5-methylphenyl)
Fluorene, 1,3-bis [2- (3-allyl-4-hydroxyphenyl) propyl] benzene, 1,4-bis [2- (3-allyl-4-hydroxyphenyl) propyl] benzene, 1,3- Dihydroxy-4-allylbenzene, 4,4'-dihydroxy-3-allylbiphenyl, 2,7-dihydroxy-3,6-diallylnaphthalene, 4,4-bis (4-hydroxyphenyl) -1,6
-Heptadiene, 1,1-bis (4-hydroxyphenyl) -3-butene, 1,1-bis (4-hydroxyphenyl) -2-propene, 1,1-bis (4-hydroxyphenyl) -2-vinyl Cyclohexane, 1,1-bis (4-hydroxyphenyl) -2-allylcyclohexane, 1,1-bis (4-hydroxyphenyl) -2-
Examples thereof include (1-cyclohexenyl) cyclohexane, and a compound represented by the following formula.

[0022]

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Of these dihydric phenols, preferred are 3,3'-diallyl-4,4'-dihydroxybiphenyl, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2 -Bis (3-allyl-4-hydroxy-5-methylphenyl) propane,
2,7-dihydroxy-3,6-diallylnaphthalene,
1,1-bis (3-allyl-4-hydroxyphenyl)
Cyclohexane, 2-allyl-1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybenzalacetophenone, and the like.

Examples of the dihydric phenol having no carbon-carbon unsaturated bond include, for example, 4,4'-dihydroxybiphenyl and 3,3'-difluoro-4,4 '
-Dihydroxybiphenyl, 4,4'-dihydroxy-
4,4′-dihydroxybiphenyls such as 3,3′-dimethylbiphenyl, 4,4′-dihydroxy-2,2′-dimethylbiphenyl, 4,4′-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-ter
t-butyl-4-hydroxyphenyl) phenylmethane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenyl) methane, bis (2-hydroxy-4methylphenyl) methane, bis (2-hydroxyphenyl) methane -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-s
ec-butylphenyl) propane, 2,2-bis (2-
(Hydroxy-4,6-dimethylphenyl) propane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2- (3-methyl-4-hydroxyphenyl) butane 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (2-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-te
rt-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) -3,3,5-trimethyl Bis (hydroxyphenyl) alkanes such as cyclohexane; bis (4-hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) ) Sulfide, bis (3-methyl-4)
Bis (4-hydroxyphenyl) sulfides such as -hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxides such as bis (4-hydroxyphenyl) sulfoxide and bis (3-methyl-4-hydroxyphenyl) sulfoxide; Bis (4-hydroxyphenyl) sulfones such as bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone; 4,4 ′ Bis (4-hydroxyphenyl) ketones such as -dihydroxybenzophenone; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-
Bis (hydroxyphenyl) fluorenes such as hydroxyphenyl) fluorene; 4,4 "-dihydroxy-
dihydroxy-p-terphenyls such as p-terphenyl; dihydroxy-p-quarterphenyls such as 4,4 '''-dihydroxy-p-quarterphenyl; 2,5-bis (4-hydroxyphenyl) pyrazine; 2,5-bis (4-hydroxyphenyl) -3,6
Bis (hydroxyphenyl) pyrazines such as -dimethylpyrazine, 2,5-bis (4-hydroxyphenyl) -2,6-diethylpyrazine; 1,8-bis (4-hydroxyphenyl) menthane, 2,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (3-methyl-
4-hydroxyphenyl) menthane, 1,8-bis (4
Bis (hydroxyphenyl) menthanes such as -hydroxy-3,5-dimethylphenyl) menthane; 1,4-
Bis [2- (4-hydroxyphenyl) -2-propyl] benzene and bis [2- (4-hydroxyphenyl) -2-propyl] benzene
(4-hydroxyphenyl) -2-propyl] benzenes; 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,
Dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene; dihydroxybenzenes such as resorcin, hydroquinone and catechol; α, ω-dihydroxypolydimethylsiloxane, α, ω-bis [3- (2- Polysiloxanes such as hydroxyphenyl) propyl] polydimethylsiloxane; 1,1,8,8-tetrahydro-1,8-dihydroxyperfluorooctane, 1,1,6,6-tetrahydro-1,6-dihydroxyperfluoro And dihydroperfluoroalkanes such as hexane.

Among these various dihydric phenols,
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 and the like are preferable,
Particularly, 2,2-bis (4-hydroxyphenyl) propane is preferable.

As the terminal terminator, a monovalent carboxylic acid and its derivative or a monovalent phenol can be used. 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. The addition ratio of these terminal stoppers is
The copolymer composition ratio is from 1 to 30 mol%, more preferably from 1 to 10 mol%. If this ratio exceeds 30 mol%, the mechanical strength may decrease. In some cases, the moldability may be reduced.

Specific examples of the 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-hydroxy Phenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [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-2,3-dihydroindole, 3,3-bis (4
-Hydroxyaryl) oxindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like.

The addition amount of these branching agents is 30 mol% or less, preferably 5 mol% or less in terms of the copolymer composition ratio, and if it exceeds 30 mol%, the moldability may be lowered. Examples of the carbonate-forming compound include various carbonyl halides such as phosgene, haloformates such as chloroformate, and carbonate compounds.
The reaction of performing polycondensation in the presence of an acid binder is usually performed in a solvent. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably employed. The proportion of the carbonate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

Examples of the acid binder 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, and organic compounds such as pyridine. 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.

Examples of the solvent used herein include aromatic hydrocarbons such as toluene and xylene, methylene chloride, chloroform, 1.1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,1 Halogenated hydrocarbons such as 2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane and chlorobenzene;
Preferred examples include 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.

As the catalyst, 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, 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.

The molecular weight of the obtained polycarbonate resin can be adjusted 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 polymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, partial decomposition treatment, etc.) to obtain a polymer having a desired molecular weight range. It may be.

The process for producing the polycarbonate resin can be carried out in various modes, for example, a dihydric phenol having a carbon-carbon unsaturated bond and / or a dihydric phenol having no carbon-carbon unsaturated bond and phosgene. To produce a polycarbonate oligomer. Then, the above-mentioned dihydric phenol having a carbon-carbon unsaturated bond and / or the dihydric phenol having no carbon-carbon unsaturated bond is added to the polycarbonate oligomer. A method in which the reaction is carried out in the presence of a mixture of a solvent and an aqueous alkali solution of an acid binder may be employed. Further, a method of reacting the above-mentioned dihydric phenol having a carbon-carbon unsaturated bond and / or dihydric phenol having no carbon-carbon unsaturated bond with phosgene in a mixed solution of the above-mentioned solvent and an aqueous alkali solution is provided. May be adopted. Usually, the former method of previously producing a polycarbonate oligomer is preferred because it is efficient.

To produce a polycarbonate oligomer, first, a dihydric phenol having a carbon-carbon unsaturated bond and / or a dihydric phenol having no carbon-carbon unsaturated bond (optionally, a branching agent ) To prepare an alkaline aqueous solution of a dihydric phenol. Subsequently, phosgene is introduced into a mixture of the aqueous alkali solution and an organic solvent such as methylene chloride to cause a reaction, and a dihydric phenol having a carbon-carbon unsaturated bond and / or having no carbon-carbon unsaturated bond is used. A polycarbonate oligomer of a dihydric phenol is synthesized. Next, the reaction solution is separated into an aqueous phase and an organic phase to obtain an organic phase containing a polycarbonate oligomer. At this time, the alkali concentration of the aqueous alkali solution is preferably in the range of 1 to 15% by weight, and the volume ratio of the organic phase to the aqueous phase is 10: 1 to 1:
10, preferably in the range of 5: 1 to 1: 5. The reaction temperature is usually 0 to 70 ° C under cooling, preferably 5 to 65 ° C.
And the reaction time is 15 minutes to 4 hours, preferably 30 minutes.
Minutes to 3 hours. The average molecular weight of the polycarbonate oligomer thus obtained is 2,000 or less,
The polymerization degree is usually 20 or less, preferably 2 to 10 mer.

The thus obtained divalent phenol having a carbon-carbon unsaturated bond and / or the dihydric phenol having no carbon-carbon unsaturated bond is added to the organic phase containing the polycarbonate oligomer thus obtained, and reacted. .
The reaction temperature is usually 10 to 50 ° C, preferably 20 to 40 ° C.
° C, and the reaction time is usually about 30 minutes to 2 hours. In this reaction, the dihydric phenol having a carbon-carbon unsaturated bond and / or the dihydric phenol having no carbon-carbon unsaturated bond is desirably added as an organic solvent solution and / or an alkaline aqueous solution. There is no particular limitation on the order of addition. . In addition, the catalyst, the terminal stopper, the branching agent, and the like in the above-described production method,
If necessary, it can be used during the production of the polycarbonate oligomer, during the subsequent reaction for increasing the molecular weight, or both.

The polycarbonate resin having a carbon-carbon unsaturated bond obtained in this manner may be a homopolymer composed of the repeating unit (1) represented by the general formula (1) or a resin represented by the general formula (1). Repeating unit (1)
And a repeating unit (2) represented by the general formula [2]. More specifically, with respect to the polycarbonate resins represented by the formulas [1] and [2], X ¹ to X 4 shown in the above formulas [1] to [4f]
Examples of the alkyl group having 1 to 10 carbon atoms represented by X ² and R ^{1 to} R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-butyl group and a t-
Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc., and the aryl group having 6 to 12 carbon atoms includes phenyl group, tolyl group, styryl Group, biphenylyl group, naphthyl group and the like. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a 2-butoxy group and a t-butoxy group. Group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like, and substituted or unsubstituted aryloxy having 6 to 12 carbon atoms. Examples of the group include a phenoxy group, a tolyloxy group, a styryloxy group, and a naphthyloxy group. Group, biphenyl oxy group. The cycloalkylidene group having 5 to 12 carbon atoms and having as a substituent a chain or cyclic hydrocarbon group having 2 to 12 carbon atoms having at least one carbon-carbon unsaturated bond represented by Y is 2-vinyl. -1,1-cyclohexylidene group, 2-allyl-1,1-cyclohexylidene group, 2- (1-cyclohexenyl) -1,1-cyclohexylidene group, 2-vinyl-1,1-cyclo Examples include a pentylidene group, a 2-allyl-1,1-cyclopentylidene group, and a 2- (1-cyclohexenyl) -1,1-cyclopentylidene group.

When the polycarbonate resin having a carbon-carbon unsaturated bond is a copolymer composed of the repeating unit (1) and the repeating unit (2), the molar ratio of the repeating unit (1) [(1 ) / ((1) + (2))]
It is 0.01 or more, preferably 0.05 to 0.3. If the molar ratio is less than 0.01, the crosslink density at the time of crosslinking is low, and the effect of improving the mechanical strength may not be sufficiently exhibited.

In addition to the repeating units (1) and (2), structural units other than those defined by the above formulas (2) and (3) may be used in the polycarbonate resin so 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 reduced viscosity [η _SP / c] of 0.01 to 10 deciliter / g measured at a temperature of 20 ° C. at a concentration of 0.5 g / deciliter using methylene chloride as a solvent. Are preferred. If the reduced viscosity [η _SP / c] is less than 0.01 deciliter / g, the mechanical strength after crosslinking may not be sufficient. If the amount exceeds 10 deciliters / g, the moldability may not be sufficient, and the viscosity of the solution may increase. The production of an electrophotographic photoreceptor by application of a liquid may be difficult.

In the method of the present invention, the polycarbonate resin having a carbon-carbon unsaturated bond is treated in the presence of one or more substances selected from transition metal catalysts, base catalysts and radical chemical species. Hydrosilylation is carried out by reacting with a silicon compound having two or more silicon-hydrogen bonds in the same molecule. The silicon compound used here is a compound represented by the formulas [4a] to [4f], and specific compounds include, for example, dimethylsilane, diethylsilane, diphenylsilane, 1,1,3,3-tetra Methyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7- Octamethyltetrasiloxane, 1,1,1,3,5,7,7,
7-octamethyltetrasiloxane, 1,4-bis (dimethylsilyl) benzene, 1,3-bis (dimethylsilyl) benzene, 1,1,3,3-tetramethyldisilazane, 1,2-bis (1, 1,3,3-tetramethyldisiloxanyl) ethane, α, ω-dihydropolydimethylsiloxane, polyphenylmethylhydrogensiloxane, methyltris (dimethylsiloxy) silane and the like.

With respect to the addition amount of these silane compounds,
Formulation in which the number of moles of silicon-hydrogen bonds in the silane compound is in the range of 0.01 to 100 equivalents, preferably 0.5 to 2 equivalents, based on the number of moles of carbon-carbon unsaturated bonds in the polycarbonate resin. It is good to choose a ratio. If the compounding ratio is less than 0.01 equivalent, the mechanical properties are not sufficiently improved by the crosslinking of the polycarbonate resin,
In addition, when added at a compounding ratio exceeding 100 equivalents, a part of the silane compound present in excess reacts with the polycarbonate bond to cause the polymer chain to be cut, and the effect of improving the mechanical properties accompanying the crosslinking is reduced. May be reduced.

As the catalyst used for the hydrosilylation reaction, a transition metal catalyst, a base catalyst and a radical chemical species can be used as described above. It is most preferable because the reaction is small and the amount of catalyst added is small. Among these transition metal catalysts, transition metal catalysts of Groups VII to X of the periodic table are preferable, and specifically, an iron catalyst [Fe (C
O) ₅ ], ruthenium catalyst [RuCl ₃ ], cobalt catalyst [Co ₂ (CO) ₈ ], rhodium catalyst [(Ph ₃ P)
₃ RhCl, (Rh (C ₂ H ₄ ) ₂ Cl) ₂ ], iridium catalyst [IrCl ₃ ], nickel catalyst [(Ph ₃ P)
₂ Ni, (Ph ₃ P) ₂ NiCl ₂ ], palladium catalyst [(Ph ₃ P) ₄ Pd, (Ph ₃ P) ₂ PdCl ₂ ],
Platinum catalyst _{[H 2 PtCl 6 · 6H 2 O} , (Ph 3 P) 4
Pt, (Pt (C ₂ H ₄ ) Cl ₂ ) ₂ , (Ph ₃ P) ₂
PtCl ₂ , Pt (C ₂ H ₄ ) (Ph ₃ P) Cl ₂ ,
(PhCN) ₂ PtCl ₂ , K ₂ PtCl ₄ , Pt-A
_{l 2 O 3, Pt-C} , platinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex, a platinum carbonyl complex, a platinum - cyclovinylmethylsiloxane complex]
And the like. Among these, Speier catalyst _{(H 2 PtCl 6 · 6H 2} O- isopropanol solution)
And platinum-1,1,3,3-tetramethyl-1,3-
Divinyldisiloxane complexes are particularly preferred.

As the base catalyst, for example, various trialkylamines such as trimethylamine and triethylamine can be used. Further, as the radical species, for example, benzoyl peroxide, 2,4
-Peroxides such as dichlorobenzoyl peroxide and azobisisobutyronitrile can be used.

The addition amount of these catalysts is 1 w / w carbon-carbon unsaturated bond of the polycarbonate resin.
tPPM〜1 wt%, preferably 100-1000 wt
In the range of PPM, it is appropriately selected in consideration of reactivity. If the amount of the catalyst is less than 1 wt PPM, the reaction rate is low and the crosslinking reaction may not proceed. If the content exceeds 1% by weight, the obtained product may be colored. Therefore, it is appropriate to set the content within the above range.

Further, the temperature during the reaction is from 20 to 20.
It is suitable to carry out at 0 ° C, preferably at 50-150 ° C. If the reaction temperature is lower than 20 ° C., the reaction rate is reduced, and if the reaction is carried out at 200 ° C. or higher, there is no effect corresponding thereto, and it is rather uneconomical. The reaction time is 1 second to 24 hours, preferably 1 minute to 12 hours. If the reaction time is less than 1 second, the reaction may not proceed sufficiently, and it is not economical to spend more than 24 hours.

The crosslinked polycarbonate resin of the present invention thus obtained is, for example, silicon-containing in the same molecule.
In a silicon compound having two or more hydrogen bonds, one silicon-hydrogen bond is bonded to a carbon-carbon unsaturated bond in the molecular chain of the polycarbonate resin having the carbon-carbon unsaturated bond, and Subsequent silicon-hydrogen bonds have a bonding site in the form of bonding to a carbon-carbon unsaturated bond in another polycarbonate molecular chain, and such a bonding site is formed between many polycarbonate molecular chains. .

The cross-linked structure of the cross-linked polycarbonate resin of the present invention includes the chemical structure of the polycarbonate resin having a carbon-carbon unsaturated bond used for cross-linking, in particular, the bonding site and the number of the unsaturated bond to the polycarbonate molecular chain, Have various forms depending on the chemical structure of Specific examples of the structure of the crosslinked polycarbonate resin of the present invention include the following.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[Wherein Ar ² , X ¹ , R ¹ , R ² ,
p, q, r, s, c, d, e, and t are represented by the formulas [1] to [1].
Has the same meaning as in [2d], wherein W is

[0057]

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(Where R ⁷ , i, m, n, t, u, v,
w is a group represented by the above formulas [2d] to [4f]. The crosslinked polycarbonate resin of the present invention reacted and hydrosilylated in this manner retains high transparency and is suitable for a material requiring high transparency.
In addition, mechanical properties such as heat resistance, impact resistance, and wear resistance,
In addition, because of its excellent electrical insulation properties, components and parts of electrical equipment, electronic equipment, optical equipment, etc., which are required to have these various properties, automotive parts, coating materials for metal or woodwork products It can be used as a highly useful material in a wide range of industrial fields such as paints.

Next, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer has a surface layer containing the above-mentioned crosslinked polycarbonate resin. is there. The electrophotographic photoreceptor of the present invention is
As long as such a photosensitive layer is formed on a conductive substrate, its structure is not particularly limited, and various types of known electrophotographic photoreceptors such as a single layer type and a multilayer type may be used. It may be good. Usually, the photosensitive layer has at least one charge generation layer and at least one charge-forming layer forming a surface layer.
A layered electrophotographic photoreceptor having a charge transport layer is preferable, and the crosslinked polycarbonate resin is preferably used as a binder resin and / or as the surface layer in at least one charge transport layer.

When the crosslinked polycarbonate resin is used as a binder resin in the electrophotographic photoreceptor of the present invention, the crosslinked polycarbonate resin may be used alone or in combination of two or more. You may use together with other resin components, such as a polycarbonate resin, as long as the objective of this invention is not obstructed. As the conductive substrate used in the electrophotographic photoreceptor of the present invention, various types such as known ones can be used, and specifically, aluminum, nickel, chromium, palladium,
Titanium, molybdenum, indium, gold, platinum, silver, copper,
Plates, drums and sheets made of zinc, brass, stainless steel, lead oxide, tin oxide, indium oxide, ITO or graphite, and glass that has been subjected to conductive treatment by coating by vapor deposition, sputtering, coating, etc.
Fabric, paper or plastic films, sheets and seamless belts, and plastic films, sheets and seamless belts laminated with metal foils such as aluminum and film-like sheets and seamless belts of metal plates, and metal oxidation treatments such as electrode oxidation A metal drum 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 base substrate 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 known substances can be used. Specific compounds include selenium alone such as amorphous selenium and trigonal selenium, tellurium alone, selenium alloys such as selenium-tellurium alloy, selenium-arsenic alloy, selenium compounds such as As ₂ Se ₃ or selenium-containing compositions , Zinc oxide, cadmium sulfide, antimony sulfide, zinc sulfide, alloys such as CdS-Se, inorganic materials composed of Group 12 and 16 elements, oxide-based semiconductors such as titanium oxide, and silicon-based materials such as amorphous silicon , Τ-type metal-free 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 titanyl phthalocyanine, 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, having a black angle 2θ of 27.3 in the X-ray diffraction pattern
Metal phthalocyanine pigments such as titanyl phthalocyanine showing a strong diffraction peak at ± 0.2 degrees, cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyrylium dyes, squarium Pigments, anthantrone pigments, benzimidazole pigments, azo pigments, thioindigo pigments, quinoline pigments, lake pigments, oxazine pigments, dioxazine pigments, triphenylmethane pigments, azurenium dyes, triarylmethane dyes, xanthine dyes, thiazine dyes, thiapyrylium dyes, Examples thereof include polyvinyl carbazole and bisbenzimidazole pigments. These compounds can be used alone or as a mixture of two or more kinds as a charge generating substance.

Among these charge generating substances, the compounds represented by the following general formulas are preferred.

[0064]

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[Wherein, Z ^{1 to} Z ⁴ each independently form an aromatic hydrocarbon ring or a heterocyclic ring which may have a substituent together with two carbon atoms on the pyrrole ring. And M represents two hydrogen atoms or a metal atom or a metal compound which may have a ligand. ]

[0066]

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[Wherein, Ar ⁶ represents a t-valent residue having a conjugated system which may contain an aromatic hydrocarbon ring or a heterocyclic ring, t is a positive number of 1 or more, and Cp is an aromatic group. Represents a coupler residue having a group-based hydroxyl group, and when t is 2 or more, each Cp may be the same or different. ]

[0068]

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[Wherein, X ^{2 to} X ⁵ each independently represent an oxygen atom, a sulfur atom, or a selenium atom; R ^P and R ^Q each represent an alkyl group or an aryl group having 1 to 12 carbon atoms;
X ² or X ³ and R ^P , X ⁴ or X ⁵ and R ^Q may form a heterocyclic ring which may have a substituent. The following compounds are examples of fluorene-based disazo pigments.

[0070]

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[0071]

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[0072]

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The following compounds are used as perylene pigments.

[0074]

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[0075]

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The polycyclic quinone pigment includes the following compounds.

[0077]

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The following compounds are examples of anthantrone pigments.

[0079]

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As the dibenzopyrene quinone pigment, there are the following compounds.

[0081]

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As the pyranthrone pigment, there are the following compounds.

[0083]

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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 crosslinked polycarbonate resin of the present invention can also be used.

Next, the charge transport layer can be obtained by forming a layer formed by binding a charge transport substance with a binder resin on a layer serving as a base (for example, a charge generation layer). As a method for forming the charge transport layer, various methods such as a known method can be used, and usually, the charge transport material is dispersed or dissolved in an appropriate solvent together with the polycarbonate resin before crosslinking in the present invention. A method in which a coating liquid is applied on a predetermined base layer and dried is used. The compounding ratio of the charge transport material and the polycarbonate resin used for forming the charge transport layer is preferably 20:80 to 80:20, more preferably 30:70 to 70:30 by weight.

In the charge transport layer, the above-mentioned polycarbonate resins can be used alone or as a mixture of two or more. Further, the resins listed as the binder resin used in the charge generation layer may be used in combination with the polycarbonate resin as long as the object of the present invention is not hindered. The thickness of the charge transport layer thus formed is 5-100 microns, preferably 10-30 microns. If the thickness is less than 5 microns, the initial potential will be low,
If it exceeds micron, electrophotographic properties may be deteriorated.

As the charge transport material, various known compounds can be used. 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, 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, polyvinylanthracene, polyvinyla Lysine, poly-9-vinylphenyl anthracene, pyrene - formaldehyde resin, ethylcarbazole resin, or the like polymers having these structures in the main chain or side chain is preferably used. These compounds may be used alone or in combination of two or more.

As these compounds, those represented by the following general formula can be suitably used.

[0089]

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[Wherein Ar ^{1 to} Ar ³ are each independently
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, Or represents an unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group, fused polycyclic heterocyclic group, Ar ¹ and Ar ² , Ar ² and Ar ³ , Ar
³ and Ar ¹ may form a ring. ]

[0091]

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

[0093]

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[Wherein Ar ¹ and Ar ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, 6 to 12 substituted or unsubstituted aryl groups, polycyclic hydrocarbon groups, substituted or unsubstituted fused polycyclic hydrocarbon groups, heterocyclic groups, polycyclic heterocyclic groups, fused polycyclic hetero groups It represents a cyclic group, and Ar ¹ and Ar ² may form a ring. R ^A is the above formula

Have the same meanings as R ^A in [9], R ^B represents an ethylene group or an ethynylene group, E is an integer of 0-4. ]

[0095]

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[Wherein Ar ¹ and Ar ² are the same as those of the above formula [1]
Have the same meaning as Ar ¹ in 0], Ar ¹ and Ar
² may form a ring. R ^A is the above formula

In [9]
R in ^AHas the same meaning as^F, R^GAre independent
A hydrogen atom, a halogen atom or an alkyl having 1 to 6 carbon atoms
And E is an integer of 0-4. ]

[0097]

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[Wherein, Ar¹~ Ar^FiveIs the above formula [1
0]¹Has the same meaning as⁶, Ar
⁷Are each independently a substituted or unsubstituted C 1 -C 6
Alkylene group, or substitution of 6 to 12 carbon atoms or
Unsubstituted aryl compounds, polycyclic hydrocarbons, substituted or unsubstituted
Is an unsubstituted fused polycyclic hydrocarbon, heterocyclic compound, polycyclic system
Shows divalent residues of heterocyclic compounds and condensed polycyclic heterocyclic compounds.
And Ar¹And Ar^Two, Ar ^ThreeAnd Ar^FourMeans a ring
May be. ]

[0099]

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[In the formula, Ar ^{1 to} Ar ⁴ are the same as those in the formula [1]
Have the same meaning as Ar ¹ in 0], Ar ¹ and Ar
² , Ar ³ and Ar ⁴ may form a ring. R
^H and ^RI are the above formulas

It has the same meaning as ^RA in [9], and E and F are each independently an integer of 0 to 4. ]

[0101]

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[Wherein, Ar ^{1 to} Ar ⁴ represent the above-mentioned formula [1]
Have the same meaning as Ar ¹ in 0], Ar ¹ and Ar
² , Ar ³ and Ar ⁴ may form a ring. R
^{A to} R ^C are the above formulas

It has the same meaning as R ^A in [9], and E to G are each independently an integer of 0 to 4. X ¹
Is -O-, -S-, -Se-, -Te-, -CR ^J R
^{K -, - SiR J R K} -, - NR J -, - PR J - ( provided that, R ^J, R ^K are each independently a hydrogen atom, a halogen atom, an alkylamino group, an arylamino group, aralkylamino group A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, Substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group, or fused polycyclic heterocyclic group). ]

[0103]

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[In the formula, Ar ¹ and Ar ² are the same as those in the formula [1]
Have the same meaning as Ar ¹ in 0], Ar ¹ and Ar
² may form a ring. R ^A is the above formula

[9]
Has the same meaning as ^RA in ^A, and A is an integer of 0 to 5. ]

[0105]

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[Wherein Ar ^{1 to} Ar ⁵ are the same as those of the above formula [1]
0] has the same meaning as Ar ¹ in R ¹ , R ^A , R
^B is the above formula

R in [9]^AHas the same meaning as
Ar¹And Ar ^Two, Ar^ThreeAnd Ar^FourIs a ring
You may. ]

[0107]

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[0108] wherein, Ar ¹ has the same meaning as Ar ¹ in formula (10), R ^A to R ^C is the formula

It has the same meaning as R ^A in [9], n is 0 or 1, and A to C are integers of 0 to 5. ]

[0109]

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[Wherein, Ar ^{1 to} Ar ³ represent the above-mentioned formula [1]
0] has the same meaning as Ar ¹ in R ^{A to} R
^C is the above formula

It has the same meaning as R ^A in [9] (where R ^B may be a hydrogen atom), n is 0 or 1, E is an integer of 0 to 4, and H is 0 to 3. It is an integer. ]

[0111]

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[Wherein Ar ¹ and Ar ² are the same as those of the above formula [1]
Have the same meaning as Ar ¹ in 0], Ar ¹ and Ar
² may form a ring. ]

[0113]

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[In the formula, Ar ^{1 to} Ar ³ are the same as those in the formula [1]
Have the same meaning as Ar ¹ in 0], Ar ¹ and Ar
² may form a ring. ]

[0115]

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[Wherein R ^{A to} R ^D , R ^I and R ^J represent the above formulas

Has the same meaning as R ^A in [9], and A to D;
I and J are each independently an integer of 0 to 5. ]

[0117]

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[In the formula, Ar ^{1 to} Ar ⁴ are the same as those in the formula [1]
0] has the same meaning as Ar ¹ and Ar ⁶ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl compound having 6 to 12 carbon atoms, polycyclic carbon Hydrogen, a divalent residue of a substituted or unsubstituted fused polycyclic hydrocarbon, a heterocyclic compound, a polycyclic heterocyclic compound, a fused polycyclic heterocyclic compound, and Ar ¹ and A
r ² , Ar ³ and Ar ⁴ may form a ring,
n is 0 or 1. ]

[0119]

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[Wherein R ^{L to} R ^O represent the above formula

It has the same meaning as ^RA in [9]. Specifically, the following compounds are used.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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In the electrophotographic photoreceptor of the present invention, an undercoat layer as 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 undercoat layer has a thickness of 0.01 to 10 microns, preferably 0.01 to 1 micron. 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-enhancing agent were added to the charge generation layer and the charge transport layer. 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.

Examples of the binder include silicone resin, polyamide resin, polyurethane resin, polyester resin,
Epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, 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 used in an amount of 5 to 5% with respect to the charge transport material.
Preferably, it is added in a blending ratio of 200% by weight.
0-100% by weight is more preferred. If the amount of the binder is less than 5% by weight, the coating of the photosensitive layer tends to be non-uniform and the image quality tends to be poor. If it exceeds 200% by weight, the sensitivity tends to decrease and the residual potential tends to increase. Specific examples of the plasticizer include biphenyl, biphenyl chloride, o
-Terphenyl, halogenated paraffin, dimethyl naphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate,
Examples include dimethyl glycol phthalate, methyl naphthalene, benzophenone, polypropylene, polystyrene, fluorohydrocarbon and the like.

Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like. Examples of the fluidity-imparting agent include Modaflow and Acronal 4F.
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.

For improving the surface properties, ethylene tetrafluoride resin, ethylene trifluoride chloride resin, ethylene tetrafluoride hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride dichloride 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.

Examples of the antioxidant include a hindered phenol antioxidant, an aromatic amine antioxidant, a hindered amine antioxidant, a sulfide antioxidant,
Organic phosphoric acid antioxidants are preferred. The mixing ratio of these antioxidants is usually
It is 0.01 to 10% by weight, preferably 0.1 to 2% by weight.

Examples of the hindered phenol-based antioxidants include the following.

[0179]

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[0180]

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[0181]

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The following are examples of the aromatic amine antioxidant.

[0183]

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Examples of hindered amine antioxidants include the following.

[0185]

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Examples of the sulfide antioxidants include the following.

[0187]

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Examples of the organic phosphorus antioxidants include the following.

[0189]

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Further, examples of the antioxidant having a hindered phenol structural unit and a hindered amine structural unit in the same molecule include the following.

[0191]

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These antioxidants may be used alone or in a combination of two or more. These may be used in addition to the photosensitive layer, a surface protective layer, an undercoat layer, and a blocking layer. May be added. As the solvent used in forming the charge generation layer and the charge transport layer, 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, ethyl acetate and esters such as ethyl cellosolve, carbon tetrachloride, chloroform,
Examples thereof include halogenated hydrocarbons such as 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 of forming the charge transport layer, the charge transport material, the additive, the polycarbonate resin having a carbon-carbon unsaturated bond used for forming the binder resin, the silicon compound, and the catalyst are used. A coating solution prepared by dispersing or dissolving in a solvent is prepared, and this is coated on, for example, the charge generation layer serving as a predetermined base, and the carbon-carbon unsaturated bonds in the polycarbonate resin are hydrosilylated, A charge-transporting layer is formed in a form in which a polycarbonate resin having a crosslinked polymer chain coexists with a charge-transporting substance as a binder resin. Here, the catalyst may be added after forming the charge transport layer without being added to the coating liquid.

As a method for preparing the coating liquid, the above-mentioned prepared raw material can be dispersed or dissolved using a ball mill, ultrasonic wave, paint shaker, red devil, sand mill, mixer, 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 formed by the above-mentioned charge transporting material, charge transporting material, additive, polycarbonate resin having a carbon-carbon unsaturated bond used for forming the binder resin, silicon resin, or the like. This is carried out by applying a solution in which a compound or a catalyst is dispersed or dissolved in a solvent to a predetermined base, and hydrosilylating carbon-carbon unsaturated bonds in the polycarbonate resin. The preparation of the coating liquid in this case, its coating method, additives and the like are the same as in the case of the formation of the photosensitive layer of 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. It is preferable to use the crosslinked polycarbonate resin of the present invention also for forming these layers.

The thickness of the photosensitive layer in the single-layer type electrophotographic photosensitive member 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 the thickness 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. The ratio of the charge transporting material to the binder resin is 10:90 to 80:20 by weight, preferably 30:70 to 70:30.

Next, the polycarbonate resin having a carbon-carbon unsaturated bond in the coating film formed by coating as described above is reacted with a silicon compound. In this case, the reaction temperature is 20 to 200 ° C. , Preferably 50 to 150 ° C, and the reaction time is 1 second to 24 hours, preferably 1 minute to
12 hours. The electrophotographic photoreceptor of the present invention thus obtained is a photoreceptor having excellent abrasion resistance and maintaining excellent printing durability and electrophotographic characteristics over a long period of time. Color, full color;
Analog, digital) printer (laser, LED,
It is suitably used in various electrophotographic fields such as a liquid crystal shutter, a facsimile, and a plate making machine.

When using the electrophotographic photoreceptor of the present invention, corona discharge (corotron, scorotron), contact charging (charging roll, charging brush) and the like are used for charging. 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 or a wet development method such as cascade development, two-component magnetic brush development, one-component insulating toner development, or one-component conductive toner development 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.

[0199]

The present invention will be described more specifically with reference to the following examples. Example 1 (1) Production of polycarbonate resin having carbon-carbon unsaturated bond 2,2-bis (4-hydroxyphenyl) propane 74
g in a solution of 550 ml of a 6% by weight aqueous sodium hydroxide solution, 250 ml of methylene chloride was added, and while stirring, phosgene gas was blown into the solution at a rate of 950 ml / min for 15 minutes while cooling. . Then, the reaction solution was allowed to stand, and the organic layer was separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 4 and a molecular terminal having a chloroformate group.

To 200 ml of a methylene chloride solution of this polycarbonate oligomer, methylene chloride was added to make a total amount of 450 ml.
20.6 g of -bis (3-allyl-4-hydroxyphenyl) propane was mixed with 150 ml of an 8% by weight aqueous sodium hydroxide solution, and 2.0 g of p-tert-butylphenol was further added as a molecular weight regulator. Next, while vigorously stirring this mixture, 2 ml of a 7% by weight aqueous solution of triethylamine was added as a catalyst, and the mixture was reacted at 28 ° C. with stirring for 1.5 hours. After completion of the reaction, the reaction product was diluted with 1 liter of methylene chloride, and then diluted twice with 1.5 liter of water for 0.02.
After washing once with 1 liter of 1N hydrochloric acid and then twice with 1 liter of water, the organic layer is poured into methanol, and the precipitated solid is filtered and dried to obtain a polycarbonate resin. Was. The polycarbonate resin obtained above had a concentration of 0.1 using methylene chloride as a solvent.
The reduced viscosity [ηsp / of the solution of 5 g / deciliter measured at 20 ° C. (measured under the same conditions in the following examples)
c] was 0.89 deciliter / g. The measurement of the reduced viscosity is performed by an automatic viscosity measuring device VMR-042 manufactured by Rigosha
Ubbelohde improved viscometer for automatic viscosity (RM
(Type). In the ¹ H-NMR spectrum measured for this polycarbonate resin, 3.
Absorption peaks based on allyl groups were observed at 5 ppm and 5.1 ppm, and absorption peaks based on wholly aromatics were observed at 7 to 8 ppm.
Calculate the copolymer composition of the repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane and the repeating unit derived from [b] 2,2-bis (3-allyl-4-hydroxyphenyl) propane As a result, [a]: [b] =
0.85: 0.15.

(2) Production of Crosslinked Polycarbonate Resin Next, the polycarbonate resin obtained in the above (1) was prepared in 0.1%.
5 g and 0.065 g of 1,4-bis (dimethylsilyl) benzene as a silicon compound were dissolved in 5 ml of methylene chloride, and platinum-1,1,3,3 was used as a catalyst.
3-tetramethyldivinyldisiloxane complex 0.002
g of a xylene solution (concentration: 5% by weight) was added, and this was cast-formed on a polyethylene terephthalate film using an applicator. Then, this was air-dried for 1 hour, heated to 120 ° C., reacted at normal pressure for 2 hours, and further dried at 120 ° C. and 1 mmHg for 12 hours to obtain a polycarbonate resin crosslinked by hydrosilylation. A film was obtained.

The crosslinked polycarbonate resin thus obtained was subjected to infrared absorption spectroscopy analysis.
The absorption due to the expansion and contraction of the vinyl group at 0 cm ^-1 disappeared, which suggests that the allyl group present in the polycarbonate resin before the crosslinking reaction was saturated by the crosslinking reaction and changed to a trimethylene bond. Can be Therefore, it was recognized that the chemical structure of this crosslinked polycarbonate resin was as follows.

[0203]

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(3) Evaluation of Crosslinked Polycarbonate For the crosslinked polycarbonate resin film obtained in the above (2), the transmittance of visible light was measured in order to evaluate the transparency, and a Suga tester manufactured by Suga Test Instruments Co., Ltd. was measured. An abrasion resistance evaluation test was performed using a wear tester NUS-ISO-3 type. The conditions of the abrasion test were as follows: a sample was reciprocated 2,000 times on abraded paper (manufactured by Suga Test Instruments; containing alumina particles having a particle diameter of 3 microns) with a load of 500 g, and the weight loss of the sample was measured. Was adopted. The results are shown in Table 1. In the transparency column in Table 1, a mark with a circle indicates that the light transmittance in the entire wavelength range of 350 to 600 nm was 90% or more, and a mark with a cross was displayed. Some are 350-60
This indicates that there was a wavelength range where the light transmittance was less than 90% in the wavelength range of 0 nm.

Example 2 (1) Production of polycarbonate resin having carbon-carbon unsaturated bond In place of 2,2-bis (3-allyl-4-hydroxyphenyl) propane used in Example 1, 3,3 A polycarbonate resin was obtained in the same manner as in Example 1, except that 17.8 g of '-diallyl-4,4'-dihydroxybiphenyl was used. The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.86 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum,
As a result of calculating the copolymer composition of this polycarbonate resin from the intensity ratio between the absorption peaks based on 3.5 ppm and 5.1 ppm allyl groups and the absorption peak based on 7 to 8 ppm total aromatic hydrogen, [a] 2 A repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane;
[B] a repeating unit derived from 3,3′-diallyl-4,4′-dihydroxybiphenyl is represented by [a]: [b] =
0.85: 0.15.

(2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was found to be as follows.

[0207]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1.

Example 3 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 1,1-bis (4 -Hydroxyphenyl) cyclohexane 87 g, and instead of 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 9,9-bis (3-allyl-4-hydroxy-5) was used.
A polycarbonate resin was obtained in the same manner as in Example 1 except that 30.7 g of (-methylphenyl) fluorene was used. The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.85 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum,
As a result of calculating the copolymer composition of this polycarbonate resin from the intensity ratio of the absorption peaks based on allyl groups of 3.5 ppm and 5.1 ppm and the absorption peaks based on wholly aromatic hydrogen of 7 to 8 ppm, [a] 1, 1-bis (4-
A repeating unit derived from (hydroxyphenyl) cyclohexane and a repeating unit derived from [b] 9,9-bis (3-allyl-4-hydroxy-5-methylphenyl) fluorene are represented by [a]: [b] = 0.80: 0.20. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0210]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1.

Example 4 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 2,2-bis (3- Methyl-4-
2,3- (hydroxyphenyl) propane
Instead of bis (3-allyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl)-
A polycarbonate resin was obtained in the same manner as in Example 1, except that 12.8 g of 1-phenylethane and 5.5 g of 2,7-dihydroxy-3,6-diallylnaphthalene were used. The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.83 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum,
The absorption peaks based on 3.5 ppm and 5.1 ppm allyl groups and the absorption peak based on 1.7 ppm 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 7-8 ppm total aromatic hydrogen As a result of calculating the copolymer composition of this polycarbonate resin from the intensity ratio of the absorption peaks based on [a] 2,2-bis (3-methyl-
A repeating unit derived from 4-hydroxyphenyl) propane, and [b] 1,1-bis (4-hydroxyphenyl)
A repeating unit derived from -1-phenylethane and [c] a repeating unit derived from 2,7-dihydroxy-3,6-diallylnaphthalene are represented by [a]: [b]:
[C] = 0.85: 0.10: 0.05. (2) Production of crosslinked polycarbonate resin A silicon compound was reacted with the polycarbonate resin obtained in (1) in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0213]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1.

Example 5 (1) Production of polycarbonate resin having carbon-carbon unsaturated bond In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 1,1,1,3,3 Using 109 g of 3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4) was used.
Instead of -hydroxyphenyl) propane, 6.5 g of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane and 17.4 g of 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane were used. Other than the above, a polycarbonate resin was obtained in the same manner as in Example 1. The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.78 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum,
3.5 ppm and 5.1 ppm absorption peaks based on allyl groups, 6.8 ppm absorption peaks based on 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, and 7-8 ppm wholly aromatic hydrogen As a result of calculating the copolymer composition of this polycarbonate resin from the intensity ratio of the absorption peak based on [a] 1,1,1,3,3,3
A repeating unit derived from hexafluoro-2,2-bis (4-hydroxyphenyl) propane, and [b] 2,2
A repeating unit derived from -bis (3-phenyl-4-hydroxyphenyl) propane and [c] a repeating unit derived from 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane are represented by [a] : [B]: [c]
= 0.80: 0.05: 0.15. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0216]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 6 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond 3,3-bis (4-hydroxyphenyl) in place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1 Using 73 g of -1-propene, 23.6 g of bis (4-hydroxyphenyl) diphenylmethane instead of 2,2-bis (3-allyl-4-hydroxyphenyl) propane and the following silicone-modified bisphenol 1
A polycarbonate resin was obtained in the same manner as in Example 1 except that g was used.

[0218]

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[0219] The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.85 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum, an absorption peak based on a vinyl group of 5 ppm and 0 pp
As a result of calculating the copolymer composition of this polycarbonate resin from the intensity ratio of the absorption peak based on the above-mentioned silicone-modified bisphenol and the absorption peak based on wholly aromatic hydrogen of 7 to 8 ppm, [a] 3,3-bis ( A repeating unit derived from 4-hydroxyphenyl) -1-propene, [b] a repeating unit derived from bis (4-hydroxyphenyl) diphenylmethane, and [c] a repeating unit derived from the silicone-modified bisphenol,
[A]: [b]: [c] = 0.85: 0.149: 0.
001. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0220]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 7 (1) Production of Polycarbonate Resin Having Carbon-Carbon Unsaturated Bond 4,4′-Dihydroxybenzalacetophenone [alias] in place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1 4,4'-dihydroxychalcone], 9.4 g of 4,4'-dihydroxybenzophenone and 4,4'-dihydroxydiphenyl ether in place of 2,2-bis (3-allyl-4-hydroxyphenyl) propane A polycarbonate resin was obtained in the same manner as in Example 1 except that 4.6 g was used.

The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.84 deciliter / g. Further, the copolymer composition of the polycarbonate resin includes (a) a repeating unit derived from 4,4′-dihydroxybenzophenone, (b) a repeating unit derived from 4,4′-dihydroxydiphenyl ether, and (c)
The repeating unit derived from 4,4′-dihydroxybenzalacetophenone is [a]: [b]: [c] = 0.1
0: 0.005: 0.85. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. In the result of infrared absorption spectrum analysis of this crosslinked polycarbonate resin,
Since the absorption at 1620 cm ⁻¹ based on the expansion and contraction of the vinyl group observed in the polycarbonate resin before crosslinking has disappeared, the chemical structure of this crosslinked polycarbonate resin is
It was found that:

[0223]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 8 (1) Production of Polycarbonate Resin Having Carbon-Carbon Unsaturated Bond Instead of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 1,3-bis [2- (4- Hydroxyphenyl) propyl] benzene 112 g,
2,2-bis (3-allyl-4-hydroxyphenyl)
7. 4,4'-dihydroxysulfone instead of propane
A polycarbonate resin was obtained in the same manner as in Example 1 except that 5 g and 2-allyl-1,1-bis (4-hydroxyphenyl) cyclohexane 10.5 g were used.

[0225] The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.78 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum, an absorption peak based on an allyl group at 3.5 ppm and 5.1 ppm and a 1,3-bis (2-
As a result of calculating the copolymer composition of this polycarbonate resin from the intensity ratio of the absorption peak based on (4-hydroxyphenyl) propyl) benzene and the absorption peak based on 7 to 8 ppm of total aromatic hydrogen, [a] 1,3- Screw [2
A repeating unit derived from-(4-hydroxyphenyl) propyl] benzene, a repeating unit derived from [b] 4,4'-dihydroxysulfone, and [c] 2-allyl-1,1-bis (4-hydroxy A repeating unit derived from phenyl) cyclohexane is represented by [a]: [b]:
[C] = 0.80: 0.10: 0.10. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0226]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 9 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond 4,4′-dihydroxybiphenyl is used in place of 2,2-bis (3-allyl-4-hydroxyphenyl) propane used in Example 1. A polycarbonate resin was obtained in the same manner as in Example 1, except that 12.3 g and 10 g of the following silicone-modified bisphenol were used.

[0228]

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The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.78 deciliter / g. Further, as a result of measuring the ¹ H-NMR spectrum, it was found that the absorption peak based on the silicone-modified bisphenol was 0 ppm and the 2,2-bis (4-
As a result of calculating the copolymer composition of this polycarbonate resin from the intensity ratio of the absorption peak based on (hydroxyphenyl) propane and the absorption peak based on total aromatic hydrogen of 7 to 8 ppm, [a] 2,2-bis (4-hydroxy A repeating unit derived from phenyl) propane;
A repeating unit derived from 4′-dihydroxybiphenyl,
And [c] the repeating unit derived from the silicone-modified bisphenol is [a]: [b]: [c] = 0.8
5: 0.14: 0.01. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0230]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 10 (1) Production of polycarbonate resin having carbon-carbon unsaturated bond Instead of 2,2-bis (3-allyl-4-hydroxyphenyl) propane used in Example 1, 2,2-bis (3 −
Phenyl-4-hydroxyphenyl) propane 16.7
g and the following silicone compound 20 g, and a polycarbonate resin was obtained in the same manner as in Example 1.

[0232]

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The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.78 deciliter / g. Further, as a result of measuring the ¹ H-NMR spectrum, the absorption peak based on the silicone compound at 0 ppm, the absorption peak based on 2,2-bis (4-hydroxyphenyl) propane at 1.7 ppm, and 6.8 pp
As a result of calculating the copolymer composition of the polycarbonate resin from the intensity ratio of the absorption peak based on m of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane,
[A] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane, and [b] a 2,2-bis (3-
[A]: [b]: [c] = 0.8. The repeating unit derived from phenyl-4-hydroxyphenyl) propane and [c] the repeating unit derived from the silicone compound
5: 0.10: 0.05. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0234]

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(3) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (2) was evaluated for transparency and abrasion resistance in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 11 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In place of 2,2-bis (3-allyl-4-hydroxyphenyl) propane used in Example 1, 2,2-bis (4 −
(5.2 g of hydroxyphenyl) propane, and
A polycarbonate resin was obtained in the same manner as in Example 1, except that 11.8 g of 2-allylphenol was used instead of p-tert-butylphenol used as a molecular weight regulator.

The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.18 deciliter / g. In addition, as a result of measuring the ¹ H-NMR spectrum, the intensity of the absorption peak based on 3.5 ppm and 5.1 ppm allyl group and the intensity of the absorption peak based on 1.7 ppm 2,2-bis (4-hydroxyphenyl) propane were measured. As a result of calculating the copolymer composition of this polycarbonate resin from the ratio, [a] 2,2-bis (4-hydroxyphenyl)
The repeating unit derived from propane and the repeating unit derived from [b] 2-allylphenol are represented by [a]: [b] =
0.82: 0.18. (2) Production of Crosslinked Polycarbonate Resin The polycarbonate resin obtained in the above (1) was reacted with a silicon compound in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. The chemical structure of the obtained crosslinked polycarbonate resin was as follows.

[0237]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 12 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In the same manner as in Example 2, a polycarbonate resin was produced. (2) Production of crosslinked polycarbonate resin 0.12 g of diphenylsilane was reacted with 0.5 g of the polycarbonate resin obtained in (1) in the same manner as in (2) of Example 1 to produce a crosslinked polycarbonate resin. . The crosslinked polycarbonate resin thus obtained had the following structure.

[0239]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 13 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In the same manner as in Example 2, a polycarbonate resin was produced. (2) Production of crosslinked polycarbonate resin To 0.5 g of the polycarbonate resin obtained in the above (1), in the same manner as in (2) of Example 1, 1,1,3,3-
0.09 g of tetramethyldisiloxane was reacted to produce a crosslinked polycarbonate resin. The crosslinked polycarbonate resin thus obtained had the following structure.

[0241]

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(3) Evaluation of Crosslinked Polycarbonate The crosslinked polycarbonate resin obtained in the above (2) was evaluated for transparency and abrasion resistance in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 14 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In the same manner as in Example 2, a polycarbonate resin was produced. (2) Production of crosslinked polycarbonate resin To 1,5,3,3, in the same manner as in (2) of Example 1, with respect to 0.5 g of the polycarbonate resin obtained in the above (1).
0.14 g of 5,5-hexamethyltrisiloxane was reacted to produce a crosslinked polycarbonate resin. The crosslinked polycarbonate resin thus obtained had the following structure.

[0243]

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(3) Evaluation of Crosslinked Polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 15 (1) Production of polycarbonate resin having carbon-carbon unsaturated bond In the same manner as in Example 2, a polycarbonate resin was produced. (2) Production of crosslinked polycarbonate resin To 0.5 g of the polycarbonate resin obtained in the above (1), in the same manner as in (2) of Example 1, 1,1,1,3,3
5,7,7,7-octamethyltetrasiloxane 0.1
95 g were reacted to produce a crosslinked polycarbonate resin. The crosslinked polycarbonate resin thus obtained had the following structure.

[0245]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 16 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In the same manner as in Example 2, a polycarbonate resin was produced. (2) Production of Crosslinked Polycarbonate Resin 0.5 g of the polycarbonate resin obtained in the above (1) was reacted with 0.045 g of the following silicon compound in the same manner as in (2) of Example 1 to obtain a crosslinked polycarbonate resin. Manufactured.

[0247]

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The crosslinked polycarbonate resin thus obtained had the following structure.

[0249]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 17 (1) Production of polycarbonate resin having carbon-carbon unsaturated bond In the same manner as in Example 2, a polycarbonate resin was produced. (2) Production of crosslinked polycarbonate resin To 0.5 g of the polycarbonate resin obtained in the above (1), in the same manner as in (2) of Example 1, 1,1,3,3-
0.09 g of tetramethyldisilazane was reacted to produce a crosslinked polycarbonate resin. The crosslinked polycarbonate resin thus obtained had the following structure.

[0251]

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(3) Evaluation of Crosslinked Polycarbonate The crosslinked polycarbonate resin obtained in the above (2) was evaluated for transparency and abrasion resistance in the same manner as in (3) of Example 1. The results are shown in Table 1. Example 18 (1) Production of a polycarbonate resin having a carbon-carbon unsaturated bond In the same manner as in Example 2, a polycarbonate resin was produced. (2) Production of crosslinked polycarbonate resin To 0.5 g of the polycarbonate resin obtained in the above (1), in the same manner as in (2) of Example 1, 1,2-bis (1,1,3,3-tetra 0.095 g of methyldisiloxanyl) ethane was reacted to produce a crosslinked polycarbonate resin. The crosslinked polycarbonate resin thus obtained had the following structure.

[0253]

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(3) Evaluation of crosslinked polycarbonate The transparency and abrasion resistance of the crosslinked polycarbonate resin obtained in the above (2) were evaluated in the same manner as in (3) of Example 1. The results are shown in Table 1.

Comparative Example 1 A polycarbonate resin was produced and cross-linked by the same method as that described in the above-mentioned JP-A-4-29314, and the transparency and abrasion resistance of the obtained cross-linked polycarbonate resin were evaluated. Did. That is, while flowing dry nitrogen gas into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a reflux condenser, 53.7 parts by weight of a 48.5% by weight aqueous sodium hydroxide solution and 230.8 parts by weight of water were added.
Parts by weight, 31.4 parts by weight of 2,2-bis (3-allyl-4-hydroxylphenyl) propane, 1,1-bis (4-
27.3 parts by weight of (hydroxyphenyl) cyclohexane was charged and dissolved. The solution was cooled to 20 ° C., and 26.2 parts by weight of phosgene gas was gradually introduced over 1 hour while stirring. Next, 8.4 parts by weight of a 48.5% by weight aqueous solution of sodium hydroxide was added, and 0.61 part by weight of p-tert-butylphenol was further added as a reaction terminator. The polymerization reaction was continued at 30 ° C. for 1 hour. After the reaction,
The methylene chloride layer was separated and acidified with hydrochloric acid, and then washed with water to remove dissolved salts. Thereafter, the methylene chloride was evaporated to obtain a solid. The reduced viscosity of this polymer was 1.2 deciliter / g.

Next, the polycarbonate resin 0.5
g, 0.05 g of pentaerythritol tetrakis (3-mercaptopropionate) as a crosslinking agent and 0.005 g of Irgacure 907 (manufactured by Ciba-Geigy)
Was dissolved in 5 ml of methylene chloride. This solution was cast on a 250 micron thick polyethylene terephthalate film using an applicator. Furthermore, after air-drying this for 1 hour,
Dry at 1 mmHg for 12 hours. The obtained sample was irradiated with a high pressure mercury lamp of 80 w / cm ² for 5 seconds,
A film of a crosslinked polycarbonate resin was obtained. The transparency and abrasion resistance of the thus obtained crosslinked polycarbonate resin were evaluated in the same manner as in (3) of Example 1 above. The results are shown in Table 1.

Comparative Example 2 0.5 g of the polycarbonate resin and 0.025 g of azobisisobutyronitrile obtained in Comparative Example 1 before the crosslinking treatment were added to 5 ml of methylene chloride and dissolved. And This coating solution was cast into a film on a 250 micron thick polyethylene terephthalate film using an applicator. Next, this was heated at 140 ° C. for 1 hour to carry out a crosslinking reaction.
By drying for a time, a crosslinked polycarbonate resin film was obtained. The transparency and abrasion resistance of the thus obtained crosslinked polycarbonate resin were evaluated in the same manner as in (3) of Example 1 above. The results are shown in Table 1.

Comparative Example 3 A reduced viscosity of 0.2 produced by using 2,2-bis (4-hydroxyphenyl) propane as a raw material dihydric phenol was 0.1.
After 77 deciliter / g of polycarbonate resin was dissolved in methylene chloride, a film was formed by a casting method.

The transparency and abrasion resistance of the thus obtained crosslinked polycarbonate resin were evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

[0260]

[Table 1]

[0261]

[Table 2]

Example 19 A polyethylene terephthalate resin film on which aluminum metal was deposited was used as a conductive substrate.
An electrophotographic photoreceptor having a laminated photosensitive layer formed by sequentially laminating a charge generation layer and a charge transport layer was 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, dispersed by a ball mill, and the dispersion was applied to the surface of the conductive substrate film by a bar coater and dried to obtain a film having a thickness of about 0.5 μm. A charge generation layer was formed.

Next, 0.5 g of 4-dibenzylamino-2-methylbenzaldehyde-1,1-diphenylhydrazone was used as a charge transporting substance, and the carbon resin obtained in (1) of Example 1 was used as a binder resin. 0.5 g of a polycarbonate resin having a carbon unsaturated bond and 1,4-bis (dimethylsilyl) benzene 0.1 as a silicon compound.
065 g was used. To this was added a solution of 0.002 g of platinum-cyclovinylmethylsiloxane complex as a catalyst in a xylene solution (platinum concentration: 3.5% by weight) and 5 ml of methylene chloride as a solvent, and dissolved to obtain a coating liquid. The coating liquid was applied on the charge generation layer by an applicator and dried. Next, this coating film was subjected to a heat treatment at 120 ° C. and normal pressure for 4 hours to carry out a crosslinking reaction of the polycarbonate resin having a carbon-carbon unsaturated bond in the coating film. In this manner, a charge transporting layer containing a methylene chloride-insoluble component (crosslinked polycarbonate resin) having a thickness of about 20 μm was formed.
For 12 hours. In the process of forming the charge transport layer, no reduction in transparency due to crystallization of the polycarbonate resin was observed until the coating liquid was applied, dried, and crosslinked.

Next, the electrophotographic characteristics of the thus obtained electrophotographic photosensitive member were evaluated. As an evaluation test apparatus, an electrostatic charging test apparatus EPA-8100 manufactured by Kawaguchi Electric Machinery Co., Ltd. was used, and the initial surface potential when corona discharge was performed at -6 kv, and 5 lux from 10 lux light irradiation.
The residual potential after half a second and the half-life exposure amount (E _1/2 ) were measured. Table 2 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 machine, a Suga abrasion tester NUS-ISO-3 type manufactured by Suga Test Machine Co., Ltd. was used, and as a condition of the abrasion test, a worn paper (containing alumina particles having a particle diameter of 3 μm) with a load of 500 g was applied. The reciprocating motion was performed 2000 times in contact with the surface of the photosensitive layer, and the weight loss was measured. Table 2 shows the results.

Examples 20 to 36 As the binder resin for the charge transport layer, the polycarbonate resin having a carbon-carbon unsaturated bond described in Examples 2 to 18 and the compound having two or more silicon-hydrogen bonds in the molecule were used. Example 19 except that each combination was used.
In the same manner as in the above, an electrophotographic photosensitive member was manufactured and evaluated. Table 2 shows the evaluation results.

Comparative Example 4 The structure of the conductive substrate and the charge generating layer and the same amount of the charge transporting substance as those of Example 1 were used as the charge transporting substance of the charge transporting layer. The uncrosslinked polycarbonate resin (0.5 g) and the crosslinking agent (0.05 g and 0.005 g, respectively) were dissolved in 5 ml of methylene chloride in the stated order to prepare a coating solution, and the crosslinking conditions were 80 w / cm ² for 5 seconds using a high-pressure mercury lamp. An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 19 except that irradiation was performed. Table 2 shows the results.

Comparative Example 5 In place of the crosslinking agent in Comparative Example 4, 0.025 g of azobisisobutyronitrile was used.
An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 19 except that the temperature was changed to 0 ° C. for 1 hour. Table 2 shows the results.

Comparative Example 6 As a binder resin for the charge transport layer, 1,1-bis (4
An electrophotographic photoreceptor was manufactured and evaluated in the same manner as in Example 19, except that a polycarbonate resin (reduced viscosity; 0.77 deciliter / g) using (-hydroxyphenyl) cyclohexane as a raw material was used. Table 2 shows the results.

[0269]

[Table 3]

[0270]

[Table 4]

[0271]

According to the method of the present invention, a crosslinked polycarbonate resin having high utility in the fields of electric equipment, electronic equipment, automobile parts, coating materials, paints, and the like can be cut by molecular cutting which causes deterioration of the polycarbonate resin in the crosslinking step. Optical and mechanical properties by crosslinking by hydrosilylation of carbon-carbon unsaturated bonds in a polycarbonate resin with a silicon compound having two or more silicon-hydrogen bonds in the molecule without causing chemical or chemical changes. A crosslinked polycarbonate resin having excellent properties, especially excellent abrasion resistance, can be produced.

Further, the electrophotographic photoreceptor of the present invention uses the above-mentioned crosslinked polycarbonate resin as a binder resin for the photosensitive layer, so that the abrasion resistance of the surface of the photosensitive layer is particularly improved and the durability is excellent.

Claims (6)

[Claims] 1. A method for preparing a polycarbonate resin having a carbon-carbon unsaturated bond in the same molecule in the presence of one or more substances selected from a transition metal catalyst, a base catalyst and a radical species. -A method for producing a crosslinked polycarbonate resin, which comprises reacting with a silicon compound having two or more hydrogen bonds for hydrosilylation. 2. The repeating unit (1) represented by the following general formula [1] or the repeating unit (1) represented by the general formula [1], wherein the polycarbonate resin having a carbon-carbon unsaturated bond is: The method for producing a crosslinked polycarbonate resin according to claim 1, which is a polycarbonate resin having a repeating unit (2) represented by the general formula [2]. Embedded image [In the formula [1], Ar ¹ is (X ¹ in the formula [1a] is a single bond, -O-, -CO-,
—S—, —SO—, —SO ₂ —, —CR ³ R ⁴ — (where R ³ and R ⁴ each independently represent a hydrogen atom,
An alkyl group, a trifluoromethyl group or a carbon number of 6 to
A substituted or unsubstituted aryl group having 12 to 12 carbon atoms, a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms, a substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, 9,9- A fluorenylidene group, a 1,8-menthanediyl group, a 2,8-menthanediyl group, a substituted or unsubstituted pyradylidene group, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, or a compound represented by the following general formula [3]: (R ⁵ in the formula [3] is independently a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms;
Which is an integer of from 1 to 6, and a group represented by formula [1a] to
A in [1c] is-(CH ₂ ) _h- , -O- (C
_{H 2) h -, - CO-} (CH 2) h -, - COO- (C
H ₂ ) a group represented by _h − (where h is an integer of 0 to 6), FG is an ethynyl group or a vinyl group, and p ¹ and p ² are integers of 0 to 4 (p. ¹ + p ² 1
And q is 1 or 2, and s
Is an integer of 1 to 6, and Y in the formula [1d] has 5 carbon atoms having a chain or cyclic hydrocarbon group having 2 to 12 carbon atoms having at least one carbon-carbon unsaturated bond as a substituent. ~ 12 cycloalkylidene groups represented by the formula [1a] ~
R ^{1 in} [1g] is a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, and R ² is the same group as R ¹ , but R ² is bonded by a hydrocarbon group having 1 to 10 carbon atoms. C in the formula [1e] is 0 or 1, e in the formula [1f] [1g] is an integer of 1 to 200, and the sum of d + e is an integer of 1 to 200. Yes, r
Are each independently an integer from 0 to 4, and t is each independently 0 to 4
6 is an integer of 6, and g is each independently an integer of 0 to 200).
² is (X ² , R ⁶ , r, t, g in the formulas [2a] to [2d]
Has the same meaning as X ¹ , R ¹ , r, t, and g, and k
Is an integer of 0 to 6). ] 3. The silicon compounds having two or more silicon-hydrogen bonds in the same molecule are represented by the following general formulas [4a] to [4f].
The method for producing a crosslinked polycarbonate according to claim 1 or 2, which is a compound represented by the formula: Embedded image [R ⁷ in the formulas [4a] to [4f] has the same meaning as R ¹ , i is an integer of 0 to 200, and n is 2 to 10
An integer of 0 and n + m is an integer of 2 to 200;
v is an integer of 0 to 200, and w is an integer of 0 to 6] 4. The catalyst according to claim 1, wherein the transition metal catalyst is one or more selected from an iron catalyst, a ruthenium catalyst, a cobalt catalyst, a rhodium catalyst, an iridium catalyst, a nickel catalyst, a palladium catalyst and a platinum catalyst. 1 to
3. The method for producing a crosslinked polycarbonate according to any one of 3. 5. A method for preparing a polycarbonate resin having a carbon-carbon unsaturated bond in the same molecule in the presence of one or more substances selected from a transition metal catalyst, a base catalyst and a radical chemical species. A crosslinked polycarbonate resin which is hydrosilylated by reacting with a silicon compound having two or more hydrogen bonds. 6. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the crosslinked polycarbonate resin according to claim 5.