JP2000017069A - Preparation of polycarbonate resin having triarylamine structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin useful as a charge transporting polymer material for an organic photoreceptor by polycondensation using a monomer having a hydroxyl group-protected triarylamine structure as a diphenol compound component. SOLUTION: A polycondensation is effected using, as a diphenol compound component, a monomer (e.g. a compound of the formula) having a triarylamine structure with its hydroxyl group protected preferably as a sulfonyl or acyl ester. Preferably the monomer having a triarylamine structure with its hydroxyl group protected is subjected to the polycondensation reaction with the protecting group removed. Thus, a problem of occurrence with time of a by-produced coloring impurity caused by the triarylamine structure of a diol compound used can be solved by maintaining stability in spite of lapse of time by protecting the dial compound, and removing the protecting group in polymerization.

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 an aromatic polycarbonate resin useful as an electrophotographic photoreceptor material.

[0002]

2. Description of the Related Art As an aromatic polycarbonate resin,
A polycarbonate resin obtained by reacting phosgene or diphenyl carbonate with 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) is known as a typical example. Such polycarbonate resins from bisphenol A are used in many fields because they have excellent properties such as transparency, heat resistance, dimensional accuracy, and mechanical strength. As one example, various studies have been made on binder resins for organic photoreceptors used in electrophotography. As a typical configuration example of the organic photoconductor, there is a laminated photoconductor in which a charge generation layer and a charge transport layer are sequentially stacked on a conductive substrate. The charge transport layer is formed of a low molecular charge transport material and a binder resin, and a number of aromatic polycarbonate resins have been proposed as the binder resin. However, the inclusion of the low-molecular charge transport material reduces the mechanical strength inherent in the binder resin, which causes deterioration of the abrasion of the photoconductor, scratches, cracks, etc., and impairs the durability of the photoconductor. Has become.

On the other hand, acrylic resins having polyvinyl anthracene, polyvinyl pyrene, poly-N-vinyl carbazole, and triphenylamine in their side chains [M. Stol
Kaet al, J. et al. Polym. Sci. , 21,9
69 (1983)] and a photoconductive polymer material such as an aromatic polycarbonate resin having a benzidine structure (JP-A-64-9964) has been studied, but has not been put to practical use.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art, and provides a method for producing an aromatic polycarbonate resin which is particularly useful as a charge transporting polymer material for an organic photoreceptor. The purpose is to provide. Further, in the production of the aromatic polycarbonate resin according to the present invention, a diol compound having a triarylamine structure is used. However, there is a problem of by-produced coloring impurities over time due to the triarylamine structure. . This is due to a decrease in the oxidation potential of the monomer. In the present invention, with respect to this problem, a high-purity aromatic polycarbonate resin is produced by protecting the diol compound to maintain stability over time, and by removing this protective group during polymerization and performing polycondensation. Another object is to provide a method.

[0005]

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by producing an aromatic polycarbonate resin by a specific method.
The present invention, that is, according to the present invention, there are provided the following methods (1) to (7) for producing an aromatic polycarbonate resin.

(1) A method for producing a polycarbonate resin, comprising polycondensing a monomer having a triarylamine structure in which a hydroxyl group is protected as a diphenol compound component.

(2) The method for producing a polycarbonate resin according to the above (1), wherein a monomer having a hydroxyl group protected as a sulfonyl or an acyl ester is used as the monomer.

(3) The polycarbonate resin according to the above (1) or (2), wherein the protecting group of the monomer having a triarylamine structure in which a hydroxyl group is protected is removed at the time of polycondensation to be subjected to a reaction. Manufacturing method.

(4) The method for producing a polycarbonate resin according to any one of the above (1) to (3), wherein the polycarbonate resin is an aromatic polycarbonate resin represented by the general formula (1).

[0010]

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Wherein Ar ¹ , Ar ² and Ar ³ are substituted or unsubstituted arylene groups, R ¹ and R ² are substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, and X is Aliphatic divalent group, cycloaliphatic divalent group, aromatic divalent group, or divalent group formed by linking these, or

[0012]

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(Where R ³ , R ⁴ , R ⁵ and R ⁶ are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom, and a and b are each independently Is an integer of 0 to 4, c and d are each independently an integer of 0 to 3, Y is a single bond, and has 2 to 1 carbon atoms.
2, a linear alkylene group, -O-, -S-, -SO
_{-, - SO 2 -, -} CO-,

[0014]

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Wherein Z ¹ and Z ² represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group. And R ⁶ and R ⁷ are bonded to form a group having 6 to 6 carbon atoms.
12 carbocyclic or heterocyclic rings;
⁶ , R ⁷ may form a carbocyclic or heterocyclic ring together with R ³ and R ^4, and R ¹³ and R ^{14 each} represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ Are each independently 1 carbon atom
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group of 5 to 5, e is an integer of 0 to 4, f is 0
G represents an integer of 0 to 2000; ) To k
Represents an integer of 5 to 5000, and j represents an integer of 0 to 5000. However, 0 <k / (k + j) ≦ 1, and the repeating unit represented by k and the repeating unit represented by j may form an alternate bonding mode. (5) The above (1) to (3), wherein the polycarbonate resin is an aromatic polycarbonate resin represented by the general formula (2).
The method for producing a polycarbonate resin according to any one of the above.

[0016]

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(Wherein, Ar ⁴ , Ar ⁵ and Ar ⁶ each represent a substituted or unsubstituted arylene group, and R ¹ , R ² , X and k and j have the same definitions as described above). (1) to (3), which are aromatic polycarbonate resins represented by the general formula (3).
The method for producing a polycarbonate resin according to any one of the above.

[0018]

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(Wherein, Ar ⁷ , Ar ⁸ and Ar ⁹ represent a substituted or unsubstituted arylene group, and R ¹ , R ² , X and k, j have the same definitions as above). (1) to (3), which are aromatic polycarbonate resins represented by the general formula (4).
The method for producing a polycarbonate resin according to any one of the above.

[0020]

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(Wherein, Ar ¹⁰ , Ar ¹¹ and Ar ¹² represent a substituted or unsubstituted arylene group, p represents an integer of 1 to 5, and R ¹ , R ² , X and k and j are the same as those described above.) As described above, according to the present invention, an aromatic polycarbonate resin having a triarylamine structure and having a charge transporting ability is produced, and further, the general formula (1), the general formula (2), and the general formula (2) An aromatic polycarbonate resin having charge transport ability represented by 3) and the general formula (4) is produced. The aromatic polycarbonate resin represented by the general formulas (1), (2), (3) and (4) is preferably a random copolymer, but may be a random block copolymer or an alternating copolymer. Good.

These aromatic polycarbonate resins have high mechanical strength and a combination of electrical, optical and mechanical properties required for a charge transport layer of an electrophotographic photosensitive member. It is.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for producing the aromatic polycarbonate resin of the present invention will be described below.

Particularly preferred monomers having a triarylamine structure used in the present invention include the following formulas (5), (6), (7) and (8).

[0025]

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[0026]

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[In the formulas (5) to (8), Ar ¹ , A
r ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , A
r ⁹ , Ar ¹⁰ , Ar ¹¹ and Ar ¹² represent a substituted or unsubstituted arylene group, R ¹ and R ² represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
p represents an integer of 1 to 5. Since these monomers have a triarylamine structure in the molecule, the oxidation potential is reduced, and coloring impurities are by-produced over time. Naturally, polymerization using an impurity-containing monomer causes problems in electrophotographic characteristics such as a decrease in sensitivity and generation of residual potential. In the present invention, the above general formulas (5), (6) and (7)
And protecting the hydroxy group of the diphenol compound represented by the general formula (8) to maintain stability over time, and removing the protecting group during polymerization to carry out polycondensation to obtain high-purity aromatics. A polycarbonate resin can be manufactured.

Although many methods for protecting the hydroxyl group are known, the easiness of the reaction and the need to remove this protecting group during polymerization, but the protecting group can be removed under mild conditions, A method must be selected in which the product does not inhibit polymerization.

From the above viewpoint, it is most preferred that the compound is protected as a sulfonyl or an acyl ester. Specific examples include acetate, benzoate, methoxy or ethoxycarbonyl derivatives, benzyloxycarbonyl derivatives, methanesulfonic acid esters, benzenesulfonic acid esters, and p-toluenesulfonic acid esters.

These protecting groups can be easily introduced by reacting with an acid chloride or an acid anhydride in the presence of a usual base.

It is necessary to remove the above protecting group at the time of polymerization, but it can be removed by treating with an aqueous alkali solution. At this time, a water-soluble solvent may be used in combination to increase the solubility of the monomer having a protecting group. However, solvents that inhibit polymerization such as alcohol must be avoided. Ether solvents such as tetrahydrofuran and dioxane are preferred.

In the production of the aromatic polycarbonate resin of the present invention, diphenols having a charge transporting ability represented by the above general formulas (5), (6), (7) and (8) are used. The compound is used as a precursor, but can be applied to a conventionally known diphenol compound.

For example, distyrylbenzene derivatives (described in JP-A-9-71642), diphenethylbenzene derivatives (described in JP-A-9-104746), α-
Phenylstilbene derivatives (described in Japanese Patent Application No. Hei 9-118893) and diphenylcyclohexane derivatives (see Japanese Unexamined Patent Application Publication No.
Japanese Patent Application Laid-Open No. Hei 9-10976), distyryltriphenylamine derivatives (described in Japanese Patent Application Laid-Open No. 9-268226), and distyryldiamine derivatives (described in Japanese Patent Application No. 9-1538).
No. 46), diphenyldistyrylbenzene derivatives (JP-A-9-221544 and JP-A-9-227669).
), Stilbene derivatives (JP-A-9-157)
378, Japanese Patent Application No. 9-162624), m
-Phenylenediamine derivatives (Japanese Patent Application Laid-Open No. 9-302084)
And resorcinol derivatives (described in JP-A-9-328439).

Further, the above general formula (5), general formula (6),
The diphenol compounds represented by the general formulas (7) and (8) are disclosed in JP-A-7-258 proposed by the present inventors.
It can be produced according to the methods described in JP-A-399-399, JP-A-8-269183, JP-A-9-151248, JP-A-9-235367 and JP-A-9-87376.

The above polycondensation is carried out using a monomer having a protected hydroxyl group. The polycarbonate resin of the present invention is produced by a method similar to the polymerization of bisphenol and a carbonic acid derivative, which is conventionally known as a method for producing a polycarbonate resin. it can. That is, at least one diphenol compound having a charge transporting ability represented by the above general formula (5), general formula (6), general formula (7) or general formula (8) is used as a precursor, It is produced by a transesterification method with an aryl carbonate, a solution with a carbonyl halide compound such as phosgene or an interfacial polymerization method, a method using a chloroformate such as bischloroformate derived from a diol, or the like. As the carbonyl halide compound, instead of phosgene, a phosgene dimer such as trichloromethylchloroformate or phosgene is used.
Bis (trichloromethyl) carbonate, which is a monomer, is also useful, and carbonyl halide compounds derived from halogens other than chlorine, for example, carbonyl bromide, carbonyl iodide, and carbonyl fluoride are also useful. These known production methods are described in, for example, a polycarbonate resin handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun). In addition, general formula (5), general formula (6),
Using a diol represented by the following general formula (9) in combination with one or more diphenol compounds having a charge transporting ability represented by the general formulas (7) and (8), An improved copolymer can be obtained. in this case,
One or more diols represented by the general formula (9) may be used in combination. The ratio of the charge transporting diphenol compound represented by the general formulas (5), (6), (7) and (8) to the diol represented by the general formula (9) is as follows: A wide range can be selected depending on the desired characteristics. In addition, random copolymers among copolymers by selecting an appropriate polymerization operation, alternating copolymer,
A block copolymer, a random alternating copolymer, a ram dam block copolymer, and the like can be obtained.

HO-X-OH (9) (where X is the same as defined above) In the interfacial polymerization, the compound is substantially insoluble in an aqueous alkaline solution of a diphenol compound and water, and dissolves polycarbonate. The reaction is carried out between the two phases with an organic solvent in the presence of a carbonate derivative and a catalyst. At this time, a polycarbonate having a narrow molecular weight distribution can be obtained in a short time by emulsifying the reaction medium by high-speed stirring or addition of an emulsifying substance. The base used in the aqueous alkali solution is an alkali metal or an alkaline earth metal, and usually,
Hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; and carbonates such as sodium carbonate, potassium carbonate, calcium carbonate and sodium hydrogen carbonate. These bases may be used alone or in combination. Preferred bases are sodium or potassium hydroxide. The water used is preferably distilled water or ion-exchanged water. The organic solvent is, for example, dichloromethane,
1,2-dichloroethane, 1,2-dichloroethylene,
Aliphatic halogenated hydrocarbons such as trichloroethane, tetrachloroethane, dichloropropane, chlorobenzene,
It is an aromatic halogenated hydrocarbon such as dichlorobenzene or a mixture thereof. Further, an organic solvent in which an aromatic hydrocarbon such as toluene, xylene, ethylbenzene or the like, an aliphatic hydrocarbon such as hexane or cyclohexane or the like may be mixed. The organic solvent is preferably an aliphatic halogenated hydrocarbon or an aromatic halogenated hydrocarbon, and more preferably dichloromethane or chlorobenzene.

The polycarbonate-forming catalyst used in the production of polycarbonate includes tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and salts thereof, and amide groups. And the like. Specific examples of the polycarbonate-forming catalyst include trimethylamine, triethylamine, tri-n-propylamine, tri-n-hexylamine, N, N, N ', N'-tetramethyl-1,4-tetramethylenediamine, and 4-pyrrolidine. Dinopyridine, N,
N'-dimethylpiperazine, N-ethylpiperidine, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium bromide, phenyltriethylammonium chloride, triethylphosphine, triphenylphosphine, diphenylbutylphosphine, tetra (hydroxymethyl ) Phosphonium chloride, benzyltriethylphosphonium chloride, benzyltriphenylphosphonium chloride, 4-methylpyridine, 1-methylimidazole,
1,2-dimethylimidazole, 3-methylpyridazine, 4,6-dimethylpyrimidine, 1-cyclohexyl-3,5-dimethylpyrazole, 2,3,5,6-tetramethylpyrazine and the like. These polycarbonate forming catalysts may be used alone or in combination. The polycarbonate forming catalyst is preferably 3
It is a tertiary amine, more preferably a tertiary amine having 3 to 30 carbon atoms in total, and particularly preferably triethylamine. These catalysts are used before adding a carbonic acid derivative such as phosgene or bischloroformate to the reaction system, and / or
It can be added after the addition.

It is desirable to use a terminal terminator as a molecular weight regulator to control the molecular weight in all the above polymerization operations. Therefore, a substituent based on the terminator is bonded to the terminal of the polycarbonate resin used in the present invention. May be. The terminating agent used is a monovalent aromatic hydroxy compound, a haloformate derivative of a monovalent aromatic hydroxy compound, a monovalent carboxylic acid or a halide derivative of a monovalent carboxylic acid. The monovalent aromatic hydroxy compound is, for example, phenol, p-cresol, o-
Ethylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol,
p-cumylphenol, p-cyclohexylphenol, p-octylphenol, p-nonylphenol,
2,4-xylenol, p-methoxyphenol, p-
Hexyloxyphenol, p-decyloxyphenol, o-chlorophenol, m-chlorophenol, p
-Chlorophenol, p-bromophenol, pentabromophenol, pentachlorophenol, p-phenylphenol, p-isopropenylphenol, 2,4
-Di (1′-methyl-1′-phenylethyl) phenol, β-naphthol, α-naphthol, p- (2 ′,
4 ', 4'-trimethylchromanyl) phenol, 2-
Phenols such as (4′-methoxyphenyl) -2- (4 ″ -hydroxyphenyl) propane or alkali metal salts and alkaline earth metal salts thereof. A haloformate derivative of a monovalent aromatic hydroxy compound is
Haloformate derivatives of the above-mentioned monovalent aromatic hydroxy compounds and the like.

The monovalent carboxylic acid is, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid, 3,3-dimethylbutyric acid , 4-methylvaleric acid, 3,
3-dimethylvaleric acid, 4-methylcaproic acid, 3,5-
Dimethylcaproic acid, fatty acids such as phenoxyacetic acid or their alkali metal salts and alkaline earth metal salts,
Benzoic acid, benzoic acid such as p-methylbenzoic acid, p-tert-butylbenzoic acid, p-butoxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid, p-chlorobenzoic acid, etc. Acids or their alkali metal and alkaline earth metal salts. Examples of the monovalent carboxylic acid halide derivative include the above-described monovalent carboxylic acid halide derivatives. These terminal blocking agents may be used alone or in combination of two or more. The terminal blocking agent is preferably a monovalent aromatic hydroxy compound, more preferably phenol, p-tert.
-Butylphenol or p-cumylphenol. The preferred molecular weight of the polycarbonate resin of the present invention is 1,000 to 500, in terms of polystyrene equivalent number average molecular weight.
000, more preferably 10,000 to 200,
000.

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

Further, an antioxidant such as hydrosulfite may be added to prevent oxidation of the diphenol compound in the aqueous alkali solution.

The reaction temperature is usually from 0 to 40 ° C., the reaction time is from several minutes to 5 hours, and the pH during the reaction is preferably maintained at usually 10 or more.

On the other hand, in solution polymerization, it is obtained by dissolving a diphenol compound in a solvent, adding a deoxidizing agent, and adding bischloroformate, phosgene or a polymer of phosgene thereto. Tertiary amines such as trimethylamine, triethylamine, tripropylamine and pyridine are used as deacidifiers. As the solvent used in the reaction, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene and chloroform, and cyclic ether solvents such as tetrahydrofuran and dioxane, and pyridine are preferable.
Further, the same molecular weight regulator and branching agent as in the case of the interfacial polymerization can be used. The reaction temperature is usually from 0 to 40 ° C, and the reaction time is from several minutes to 5 hours.

It is also produced by a transesterification method. In this case, the diphenol compound and the bisaryl carbonate are mixed in the presence of an inert gas,
React at 0-350 ° C. The degree of pressure reduction is changed stepwise, and finally, the pressure is reduced to 1 mmHg or less, and phenols produced are distilled out of the system. The reaction time is usually about 1 to 4 hours. Further, if necessary, a molecular weight regulator and an antioxidant may be added. As bisaryl carbonates, diphenyl carbonate, di-p-tolyl carbonate,
Examples include phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.

The polycarbonate resin obtained as described above contains the catalyst and antioxidant used during the polymerization, unreacted diphenol compounds and terminal terminators, and impurities such as inorganic salts generated during the polymerization. Used after removal. For these purification operations, conventionally known methods described in the aforementioned polycarbonate resin handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun) can be used.

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

Next, the contents of the general formula which is a main structural unit of the present invention will be described in more detail.

In the general formulas (1), (2), (3) and (4), R ¹ and R ² are a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Represents Examples of the substituted or unsubstituted alkyl group include the following.

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

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

In the general formulas (1), (2), (3) and (4), Ar ^{1 to} Ar ¹² represent a substituted or unsubstituted arylene group. Specifically, it represents a divalent group derived from a substituted or unsubstituted aryl group represented by R ¹ and R ² .

Although the structural units of the general formula have been described above, the same symbols have the same definitions in other general formulas.

The aromatic polycarbonate resin produced by the present invention is represented by the above general formulas (1), (2), (3) and (4).
The following shows a specific example. As the diol, for example, compounds described in a polycarbonate resin handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun) can be used. Hereinafter, specific examples of the general formula (9) will be shown.

When X in the general formulas (1) to (4) is an aliphatic divalent group or a cycloaliphatic divalent group, typical specific examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, Polyethylene glycol, polytetramethylene ether glycol, 1,3-
Propanediol, 1,4-butanediol, 1,5-
Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1 , 10-decanediol, 1,11-undecanediol, 1,12-
Dodecanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-
Propanediol, 2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, xylylene diol, 1,4-bis (2-hydroxyethyl ) Benzene, 1,4-bis (3-hydroxypropyl) benzene, 1,4-bis (4-hydroxybutyl) benzene, 1,4-bis (5-hydroxypentyl) benzene, 1,4-bis (6- (Hydroxyhexyl) benzene.

Examples of the case where X is an aromatic divalent group include a divalent group derived from a substituted or unsubstituted aryl group defined for R ¹ and R ² .
X represents a divalent group formed by linking these divalent groups or a divalent group shown below.

[0056]

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(Where R ³ , R ⁴ , R ⁵ and R ⁶ are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom, and a and b are each independently Is an integer of 0 to 4, c and d are each independently an integer of 0 to 3, Y is a single bond, and has 2 to 1 carbon atoms.
2, a linear alkylene group, -O-, -S-, -SO-,
-SO _2- , -CO-,

[0058]

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Wherein Z ¹ and Z ² represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group. R ⁶ and R ⁷ are bonded to each other to form a group having 6 carbon atoms
~ 12 carbocyclic or heterocyclic rings;
R ^6, R ⁷ is R ^3, R ⁴ jointly with may form a carbocyclic or heterocyclic ring, R ^13, R ¹⁴ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ^15, R ¹⁶ independently represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or a substituted or unsubstituted aryl group; e is an integer of 0 to 4; f is an integer of 0 to 20; Represents an integer of 2000. ) Represents a group selected from Of these, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group each represent R ¹ and R ²
And the same as the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group defined in. Further, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Z ¹ and Z ² are substituted or unsubstituted aliphatic 2
Examples of the divalent group include divalent groups obtained by removing a hydroxy group from a diol when X is an aliphatic divalent group or a cycloaliphatic divalent group. Examples of the case where Z ¹ and Z ² are substituted or unsubstituted arylene groups include divalent groups derived from substituted or unsubstituted aryl groups defined for R ¹ and R ² .

Representative specific examples of preferred diols when X is an aromatic divalent group include bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane, bis ( 3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4 -Hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl)
-1-phenylethane, 1,3-bis (4-hydroxyphenyl) -1,1-dimethylpropane, 2,2-bis (4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- ( 3-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2
-Methylpropane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2- Bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-
Hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) nonane, bis (3,5-dimethyl-4)
-Hydroxyphenyl) methane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec- Butyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert
-Butyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2, 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-
Hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy Phenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-
Bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cycloheptane, 2,2-bis (4-hydroxyphenyl) ) Norbornane, 2,2-bis (4-hydroxyphenyl) adamantane, 4,4′-dihydroxydiphenylether, 4,4′-dihydroxy-3,3′-
Dimethyl diphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-
4,4′-dihydroxydiphenyl sulfide, 3,
3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4,4'-
Dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 3,3'-dimethyl-
4,4′-dihydroxydiphenyl sulfone, 3,3 ′
-Diphenyl-4,4'-dihydroxydiphenylsulfone, 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) ketone, bis (3-methyl-4-hydroxyphenyl) ketone, 3,3,3 ', 3'-tetramethyl-6,6'-
Dihydroxyspiro (bis) indane, 3,3 ', 4
4'-tetrahydro-4,4,4 ', 4'-tetramethyl-2,2'-spirobi (2H-1-benzopyran)-
7,7'-diol, trans-2,3-bis (4-hydroxyphenyl) -2-butene, 9,9-bis (4-
(Hydroxyphenyl) fluorene, 9,9-bis (4-
Hydroxyphenyl) xanthene, 1,6-bis (4-
Hydroxyphenyl) -1,6-hexanedione, α,
α, α ′, α′-tetramethyl-α, α′-bis (4-
(Hydroxyphenyl) -p-xylene, α, α, α ′,
α'-tetramethyl-α, α'-bis (4-hydroxyphenyl) -m-xylene, 2,6-dihydroxybenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathiin , 9,10
-Dimethyl-2,7-dihydroxyphenazine, 3,6
-Dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 2,7-dihydroxypyrene, hydroquinone, resorcinol, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol -Bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, phenol-modified silicone oil and the like. Further, aromatic diol compounds containing an ester bond produced by reacting 2 mol of diol with 1 mol of isophthaloyl chloride or terephthaloyl chloride are also useful.

In the aromatic polycarbonate resins represented by the general formula (1), the general formula (2), the general formula (3) and the general formula (4), the composition ratio of the charge transporting diphenol unit and the diol unit is respectively Although shown as k and j, the composition ratio can be arbitrarily selected. In addition, the charge transporting diphenol unit and the diol unit can form a bonding mode of alternating copolymerization. However, considering the electrophotographic properties, it is desirable that the charge transporting diphenol unit is contained in an amount of preferably 5 mol% or more, more preferably 20 mol% or more of all the structural units.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0063]

EXAMPLE 1 15.5 g of 4-methyl-4 '-[4,4-bis (4-hydroxyphenyl) -1,3-butadienyl-1] triphenylamine was dissolved in 120 ml of acetic anhydride. To the mixture was added 6 ml of pyridine, and the mixture was stirred at room temperature for 1 hour. Thereafter, the content was poured into 350 ml of water, and the precipitate was filtered, washed with water and dried. This was recrystallized from a mixed solvent of toluene-n-hexane to give an ester 1 represented by the following formula of yellow needles.
0.9 g was obtained.

Melting point: 154.5 to 155.5 ° C.

[0065]

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Example 2 N-phenyl-N- {4- [4,4-bis (4-hydroxyphenyl) -1-butyl]}-9,9-dimethylfluoren-2-amine was prepared in the same manner as in Example 1. The ester of the following formula was obtained as a yellow oil.

[0067]

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Example 3 1,1-bis (4-hydroxyphenyl) -1- (4-
27.2 g of di-p-tolylaminophenyl) ethane was dissolved in 70 ml of acetic anhydride, and 16 ml of pyridine was added thereto, followed by stirring at room temperature for 30 minutes. The contents were diluted with n-hexane, filtered and dried. This was recrystallized from a mixed solvent of ethyl acetate-ethanol to obtain 18.6 g of an ester represented by the following formula as colorless needles.

Melting point: 184.0-185.0 ° C.

[0070]

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Example 4 To 5.70 g (0.01 mol) of the ester obtained in Example 3, 4.56 g (0.07 mol) of potassium hydroxide and 60 ml of water were added 20 ml of tetrahydrofuran (hereinafter referred to as THF). After the temperature was raised to 85 ° C. in a nitrogen stream (at which point the hydrolysis was completed), THF was distilled off.
The content was cooled to 3 ° C., and 0.46 g (2.0 mmol) of benzyltriethylammonium chloride was added thereto. Under vigorous stirring, 2.54 g (0.011 mol) of diethylene glycol bischloroformate was added to dehydrated methylene chloride. The solution dissolved in 60 ml is heated at 3-5 ° C for 40 minutes.
It was dropped over a minute. After stirring at room temperature for 2 hours, the organic layer was separated and washed with ion-exchanged water. A methylene chloride solution was added dropwise to 1.3 liters of methanol, and the precipitate was filtered and dried. The reprecipitation purification with methylene chloride / methanol was further repeated twice to obtain 4.67 g of an alternating copolymer polycarbonate resin represented by the following formula. The molecular weight of this resin in terms of polystyrene determined by gel permeation chromatography was 18,200 in number average molecular weight and 148,000 in weight average molecular weight. The glass transition temperature obtained from differential scanning calorimetry was 113 ° C.

Elemental analysis value (%) Actual measurement value (calculated value) C 74.83 (74.62) H 5.92 (5.80) N 2.37 (2.18) Infrared absorption spectrum (thin film method) 1 is shown in FIG.
A stretching vibration of carbonyl based on a carbonate group was observed at 60 cm- ¹ .

[0073]

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Example 5 1.48 g (2.6 mmol) of the ester obtained in Example 3, 1.19 g (18.2 mmol) of potassium hydroxide, 0.1 ml of benzyltriethylammonium chloride.
12 g (0.50 mmol) in 5 ml THF and 1 water
6 ml was added, and the temperature was raised to 85 ° C. under a nitrogen stream (at which point the hydrolysis was completed), and THF was distilled off. The content was cooled to 3 ° C., and while stirring vigorously, a solution prepared by dissolving 1.01 g (2.9 mmol) of 2,2-bis (4-hydroxyphenyl) propanebischloroformate in 16 ml of dehydrated methylene chloride was added. It was added dropwise at ５5 ° C. over 50 minutes. After stirring at room temperature for 2 hours, the organic layer was separated, washed with ion-exchanged water, a methylene chloride solution was dropped into 800 ml of methanol, and the precipitate was filtered and dried. The reprecipitation purification with methylene chloride / methanol was further repeated twice to obtain 1.40 g of an alternating copolymer polycarbonate resin represented by the following formula. The molecular weight of this resin in terms of polystyrene determined by gel permeation chromatography was 29000 in number average molecular weight and 29200 in weight average molecular weight.
It was 0. The glass transition temperature obtained by differential scanning calorimetry was 177 ° C.

Elemental analysis value (%) Actual measurement value (calculated value) C 79.82 (79.98) H 5.61 (5.66) N 1.81 (1.83) Infrared absorption spectrum (thin film method) 2 is shown in FIG.
A stretching vibration of carbonyl based on a carbonate group was observed at 75 cm- ¹ .

[0076]

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Example 6 3.99 g (7.0 mmol) of the ester obtained in Example 3, 2.07 g (49.2 mmol) of sodium hydroxide, and 6.3 mg of sodium hydrosulfite were added to T.
HF (14 ml) and water (42 ml) were added, and the mixture was cooled to 85 under a nitrogen stream.
After the temperature is raised to ℃ (hydrolysis is completed at this point) T
HF was distilled off. The content was cooled to 3 ° C., and while stirring vigorously, a solution prepared by dissolving 2.49 g (7.0 mmol) of 2,2-bis (4-hydroxyphenyl) propanebischloroformate in 42 ml of dehydrated methylene chloride was added.
It was added dropwise at ５5 ° C. over 50 minutes. Then p-tert
11 mg of -butylphenol was added, and 2 drops of triethylamine were further added, followed by stirring at room temperature for 2 hours. Methylene chloride 7
After diluting with 0 ml, the organic layer was separated, washed with a 5% aqueous sodium hydroxide solution, then with a 2% aqueous hydrochloric acid solution, washed with ion-exchanged water, and a methylene chloride solution was dropped into 2 liters of methanol to precipitate the precipitate. After filtration and drying, 4.66 g of the alternating copolymer polycarbonate resin shown in Example 5 was obtained. The molecular weight of this resin in terms of polystyrene determined by gel permeation chromatography was 2 in number average molecular weight.
The weight average molecular weight was 6,000, and the weight average molecular weight was 10,7000. The glass transition temperature obtained by differential scanning calorimetry was 17
5.8 ° C.

Elemental analysis value (%) Actual measurement value (calculated value) C 79.65 (79.98) H 5.62 (5.66) N 1.81 (1.83) Infrared absorption spectrum (thin film method) Was consistent with FIG.

Example 7 3.99 g (7.0 mmol) of the ester obtained in Example 3, 2.35 g (56.0 mmol) of sodium hydroxide and 6.0 mg of sodium hydrosulfite were added to T.
HF (10 ml) and water (40 ml) were added, and the mixture was added under a nitrogen stream.
After the temperature is raised to ℃ (hydrolysis is completed at this point) T
HF was distilled off. The contents were cooled to 11 ° C. and, with vigorous stirring, 1.25 g (4.2 mmol) of bis (trichloromethyl) carbonate was added to 25 ml of dehydrated methylene chloride.
The solution dissolved in ml was added dropwise at 5 to 11 ° C over 35 minutes. Then 11 mg of p-tert-butylphenol
Was added, and 2 drops of triethylamine were further added, followed by stirring at room temperature for 2 hours. After diluting with 50 ml of methylene chloride, the organic layer was separated, washed with a 5% aqueous sodium hydroxide solution, then with a 2% aqueous hydrochloric acid solution, and then with ion-exchanged water. The product was filtered and dried to obtain 3.00 g of a polycarbonate resin represented by the following formula. The molecular weight of this resin in terms of polystyrene by gel permeation chromatography was 24100 in number average molecular weight and 79300 in weight average molecular weight.
Met. The glass transition temperature obtained by differential scanning calorimetry was 188.2 ° C.

Elemental analysis value (%) Actual measurement value (calculated value) C 81.80 (82.16) H 5.57 (5.72) N 2.69 (2.74) Infrared absorption spectrum (thin film method) 3 is shown in FIG.
A stretching vibration of carbonyl based on a carbonate group was observed at 75 cm- ¹ .

[0081]

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Example 8 3.00 g (5.2 mmol) of the ester obtained in Example 1, 1.53 g (36.3 mmol) of sodium hydroxide and 4.6 mg of sodium hydrosulfite were added to T.
HF (12 ml) and water (32 ml) were added.
After the temperature is raised to ℃ (hydrolysis is completed at this point) T
HF was distilled off. The content was cooled to 5 ° C., and while vigorously stirring, a solution prepared by dissolving 1.84 g (5.2 mmol) of 2,2-bis (4-hydroxyphenyl) propanebischloroformate in 32 ml of dehydrated methylene chloride was added.
It was added dropwise at ５5 ° C. over 30 minutes. Then p-tert
-Butylphenol (8 mg) was added, and triethylamine (2 drops) was further added, followed by stirring at room temperature for 5 hours. Methylene chloride 50
After diluting with water, the organic layer was separated, washed with a 5% aqueous solution of sodium hydroxide, then with a 2% aqueous solution of hydrochloric acid, and then with ion-exchanged water. A methylene chloride solution was added dropwise to 2 liters of methanol. After filtration and drying, 3.55 g of an alternating copolymer polycarbonate resin represented by the following formula was obtained.
The molecular weight of this resin in terms of polystyrene determined by gel permeation chromatography was 837 in number average molecular weight.
0 and the weight average molecular weight was 20,400. The glass transition temperature obtained from differential scanning calorimetry was 173.9 ° C.
Met.

Elemental analysis value (%) Actual measurement value (calculated value) C 80.29 (80.50) H 5.30 (5.33) N 1.70 (1.81) Infrared absorption spectrum (thin film method) 4 is shown in FIG.
A stretching vibration of carbonyl based on a carbonate group was observed at 80 cm- ¹ .

[0084]

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Example 9 Instead of 2,2-bis (4-hydroxyphenyl) propane bischloroformate used in Example 8, 1.89 g of bischloroformate represented by the following formula:
(5.2 mmol)

[0086]

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The same procedure as in Example 8 was followed, except that the resin was used in the same manner as in Example 8, but the alternating copolymerized polycarbonate resin represented by the following formula:
17 g were obtained. The molecular weight of this resin in terms of polystyrene measured by gel permeation chromatography was 13,200 in number average molecular weight and 39,800 in weight average molecular weight. The glass transition temperature obtained from the differential scanning calorimetry was 56.4 ° C.

Elemental analysis value (%) Actual measurement value (calculated value) C 74.83 (74.72) H 6.84 (7.21) N 1.67 (1.77) Infrared absorption spectrum (thin film method) 5 is shown in FIG.
A stretching vibration of carbonyl based on a carbonate group was observed at 60 cm- ¹ .

[0089]

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Example 10 3.42 g (4.7 mmol) of the ester obtained in Example 2, 1.56 g (37.8 mmol) of sodium hydroxide and 4.0 mg of sodium hydrosulfite were added to T.
10 ml of HF and 30 ml of water were added, and the mixture was
After the temperature is raised to ℃ (hydrolysis is completed at this point) T
HF was distilled off. The contents were cooled to 5 ° C. and 1.08 g of 2,2-bis (4-hydroxyphenyl) propane was obtained.
(4.7 mmol) was added. A solution of 1.25 g (4.2 mmol) of bis (trichloromethyl) carbonate dissolved in 30 ml of dehydrated methylene chloride was added dropwise at 4 to 8 ° C. over 30 minutes. Then, 2 drops of triethylamine were added, and the mixture was stirred at room temperature for 2 hours. 50 ml of methylene chloride
After diluting with, the organic layer was separated, washed with a 5% aqueous sodium hydroxide solution and then with a 2% aqueous hydrochloric acid solution, and then washed with ion-exchanged water. A methylene chloride solution was added dropwise to 900 ml of methanol, and the precipitate was filtered. After drying, 4.15 g of a random copolymer polycarbonate resin represented by the following formula was obtained.
The molecular weight of this resin in terms of polystyrene by gel permeation chromatography was 130 in number average molecular weight.
The weight average molecular weight was 53,000. The glass transition temperature obtained by differential scanning calorimetry was 143.0.
° C.

Elemental analysis value (%) Actual measurement value (calculated value) C 81.90 (81.70) H 6.02 (5.83) N 1.48 (1.59) Infrared absorption spectrum (thin film method) 6 is shown in FIG.
A stretching vibration of carbonyl based on a carbonate group was observed at 75 cm- ¹ .

[0092]

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The following is an application example using the polycarbonate resin obtained by the production method according to the present invention. Application Example 1 A solution of a polyamide resin (CM-8000: manufactured by Toray) dissolved in a mixed solvent of methanol and butanol on an aluminum plate. Was applied with a doctor blade and air-dried to form a 0.3 μm intermediate layer. On this, a bisazo compound represented by the following formula as a charge generating substance was pulverized by a ball mill in a mixed solvent of cyclohexanone and 2-butanone, and the obtained dispersion was applied with a doctor blade and air-dried.
A 5 μm charge generation layer was formed.

[0094]

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Next, the polycarbonate resin obtained in Example 9 as a charge transport material was dissolved in dichloromethane.
This solution was applied onto the charge generation layer with a doctor blade, air-dried, and then dried at 120 ° C. for 20 minutes to form a charge transport layer having a thickness of 20 μm, thereby producing a photoreceptor.

For the photoreceptor thus produced, a commercially available electrostatic copying paper tester [SP42, manufactured by Kawaguchi Electric Works, Ltd.]
After allowed charged subjected to corona discharge of -6 KV for 20 seconds in the dark using an 8-inch], after the surface potential V _m of the photoconductor (V) was measured, was left at more dark for 20 seconds, the surface potential V ₀
(V) was measured. Next, a tungsten lamp light is irradiated so that the illuminance on the surface of the photoreceptor becomes 4.5 lux, a time (second) until V ₀ becomes 1/2 is obtained, and an exposure amount E _1/2 (lux · sec) was calculated. The results are shown below.

V _m = −1692 V V ₀ = −1123 V E _1/2 = 0.99 lux · sec Further, after charging the above photoreceptor by using a commercially available electrophotographic copying machine, through the original drawing, Irradiates light to form an electrostatic latent image, develops it using a dry developer, electrostatically transfers the obtained image (toner image) onto plain paper, and fixes it to obtain a clear transferred image. Was done. Similarly, when a wet type developer was used as the developer, a clear transfer image was obtained.

[0098]

As described above, according to the production method of the present invention, an aromatic polycarbonate resin useful as a charge transporting material for an electrophotographic photosensitive member can be produced.

[Brief description of the drawings]

FIG. 1 shows I of the polycarbonate resin obtained in Example 4.
R spectrum.

FIG. 2 shows I of the polycarbonate resin obtained in Example 5.
R spectrum.

FIG. 3 shows I of the polycarbonate resin obtained in Example 7.
R spectrum.

FIG. 4 shows I of the polycarbonate resin obtained in Example 8.
R spectrum.

FIG. 5 shows I of the polycarbonate resin obtained in Example 9.
R spectrum.

FIG. 6 is an IR spectrum of the polycarbonate resin obtained in Example 10.

 ──────────────────────────────────────────────────続 き Continued from the front page (72) Inventor Kazuki Nagai 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Lee Hongkook 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Shinichi Kawamura 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Susumu Suzuka 66-2 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture Inside (72) Inventor Katsuhiro Morooka 66-2 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Hodani Chemical Industry Incorporated F term (reference) 2H068 AA13 AA20 AA21 BB26 BB49 EA04 4J029 AA09 AB04 AC02 AC03 AE18 BA01 BA02 BA03 BA04 BA05 BA07 BB06A BB10A BB10B BB12A BB12B BB13A BB13B BB16A BD03A BD06A BD07A BD09A BD09B BE05A BE07 BF09 BF18 BF21 BF25 BF30 BG06X BG08X BG08Y BG17X BG20X BG25X BH01 BH02 BH04 DA08 DB07 DB11 DB13 FA07 FA16 FA20 FB03 FB07 FB15 FB19 HC01 HC01 HC01 HC01 FC01 JF031 JF041 JF141 KA01 KD01 KD07 KE03 KE05 KE09 KE11

Claims (7)

[Claims] 1. A method for producing a polycarbonate resin, comprising polycondensing a monomer having a triarylamine structure in which a hydroxyl group is protected as a diphenol compound component. 2. The method for producing a polycarbonate resin according to claim 1, wherein a monomer having a hydroxyl group protected as a sulfonyl or an acyl ester is used as the monomer. 3. The process for producing a polycarbonate resin according to claim 1, wherein the reaction is carried out by removing the protecting group of the monomer having a triarylamine structure in which the hydroxyl group is protected during the polycondensation. 4. The polycarbonate resin according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin represented by the general formula (1).
3. The method for producing a polycarbonate resin according to any one of 3. Embedded image [Wherein, Ar ¹ , Ar ² and Ar ³ represent a substituted or unsubstituted arylene group, R ¹ and R ² represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and X represents an aliphatic group. A divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or (Where R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a halogen atom, and a and b are each independently 0
And c and d are each independently an integer of 0 to 3, Y is a single bond, a linear alkylene group having 2 to 12 carbon atoms, -O-, -S-, -SO-, -SO
_2- , -CO-, Wherein Z ¹ and Z ² represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group;
⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, Represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group; R ⁶ and R ⁷ may combine to form a carbon ring or a heterocyclic ring having 6 to 12 carbon atoms; ⁶ , R ⁷ may form a carbocyclic or heterocyclic ring together with R ³ and R ^4, and R ¹³ and R ^{14 each} represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ Each independently represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or a substituted or unsubstituted aryl group; e is an integer of 0 to 4;
And g represents an integer of 0 to 2000. ) And k is 5
An integer of 5000, j represents an integer of 0 to 5000. However, 0 <k / (k + j) ≦ 1, and the repeating unit represented by k and the repeating unit represented by j may form an alternate bonding mode. ] 5. The polycarbonate resin according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin represented by the general formula (2).
3. The method for producing a polycarbonate resin according to any one of 3. Embedded image (Wherein, Ar ⁴ , Ar ⁵ and Ar ⁶ represent a substituted or unsubstituted arylene group, and R ¹ , R ² , X and k, j have the same definitions as above) 6. The polycarbonate resin according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin represented by the general formula (3).
3. The method for producing a polycarbonate resin according to any one of 3. Embedded image (In the formula, Ar ⁷ , Ar ⁸ and Ar ⁹ represent a substituted or unsubstituted arylene group, and R ¹ , R ² , X and k, j have the same definitions as described above.) 7. The polycarbonate resin according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin represented by the general formula (4).
3. The method for producing a polycarbonate resin according to any one of 3. Embedded image (In the formula, Ar ¹⁰ , Ar ¹¹ and Ar ¹² represent a substituted or unsubstituted arylene group, p represents an integer of 1 to 5, R ¹ ,
R ² , X and k, j have the same definitions as above.