JP2000026590A - Aromatic polycarbonate resin - Google Patents

Abstract

(57) [Problem] To provide an aromatic polycarbonate resin useful as a charge transporting polymer material of an organic photoreceptor for electrophotography. A polycarbonate resin containing a structural unit represented by the following general formula. Embedded image [R ¹ is H, alkyl, aryl, Ar ¹ , Ar ² , A
r ⁴ and Ar ⁵ are arylene, Ar ³ is aryl]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aromatic polycarbonate resin useful as a photosensitive material for electrophotography.

[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 novel aromatic polycarbonate resin which is particularly useful as a charge transporting polymer material for an organic photoreceptor. The purpose is to:

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by a novel aromatic polycarbonate resin containing a specific structural unit, and have accomplished the present invention.

That is, the present invention provides the following (1) to (12).

(1) A polycarbonate resin containing a structural unit represented by the following general formula (1).

[0008]

Embedded image

(Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹ , Ar ² , Ar ⁴ and Ar ⁵ represent a substituted or unsubstituted arylene group And each may be the same or different. Ar ³ represents a substituted or unsubstituted aryl group.) (2) Consisting of structural units represented by the above general formula (1) and the following general formula (2) When the composition ratio of the structural unit represented by the general formula (1) is k and the composition ratio of the structural unit represented by the general formula (2) is j, the ratio of the composition ratio is 0 <k / (k + j).
≦ 1 polycarbonate resin.

[0010]

Embedded image

[Wherein, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or

[0012]

Embedded image

(Where R ² , R ³ , R ⁴ and R ⁵ 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]

Embedded image

Wherein Y ¹ and Y 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 ² and R ^3, 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; ). (3) A polycarbonate resin comprising a repeating unit represented by the following general formula (3).

[0016]

Embedded image

(Wherein R ¹ , Ar ¹ , Ar ² , Ar ³ , Ar
^4, Ar ^5, X is the same as in the previous definition, n is an integer of at repetition number 2-5000. (4) A polycarbonate resin containing a structural unit represented by the following general formula (4).

[0018]

Embedded image

(In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ¹⁹ and R ²⁰ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group. And each may be the same or different. Ar ³ represents a substituted or unsubstituted aryl group.) (5) Consisting of the structural units represented by the general formula (4) and the general formula (2) When the composition ratio of the structural unit represented by the general formula (4) is k and the composition ratio of the structural unit represented by the general formula (2) is j, the ratio of the composition ratio is 0 <k / (k + j).
≦ 1 polycarbonate resin.

(6) A polycarbonate resin comprising a repeating unit represented by the following general formula (5).

[0021]

Embedded image

(Wherein R ¹ , R ¹⁹ , R ²⁰ , Ar ³ , X, n
Is the same as the previous definition. (7) A polycarbonate resin comprising a repeating unit represented by the following general formula (6).

[0023]

Embedded image

(In the formula, R ¹ , R ¹⁹ , R ²⁰ and Ar ³ are the same as defined above.) (8) From the structural units represented by the general formulas (6) and (2) When the composition ratio of the structural unit represented by the general formula (6) is k and the composition ratio of the structural unit represented by the general formula (2) is j, the composition ratio is 0 <k / (k + j). )
≦ 1 polycarbonate resin.

(9) A polycarbonate resin comprising a repeating unit represented by the following general formula (7).

[0026]

Embedded image

(Wherein R ¹ , R ¹⁹ , R ²⁰ , Ar ³ , X, n
Is the same as the previous definition. (10) A polycarbonate resin containing a structural unit represented by the following general formula (8).

[0028]

Embedded image

(In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ¹⁹ , R ²⁰ , and R ²¹ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted group. Which may be the same or different.) (11) Consisting of the structural units represented by the general formula (8) and the general formula (2), and represented by the general formula (8) When the composition ratio of the structural unit is k and the composition ratio of the structural unit represented by the general formula (2) is j, the composition ratio is 0 <k / (k +
j) A polycarbonate resin with ≦ 1.

(12) A polycarbonate resin comprising a repeating unit represented by the following general formula (9).

[0031]

Embedded image

(Wherein R ¹ , R ¹⁹ , R ²⁰ , R ²¹ , X, n
Is the same as the previous definition. As described above, the aromatic polycarbonate resin of the present invention has a charge transporting ability. The structural unit represented by the general formula (1), the general formula (4), the general formula (6) or the general formula (8) And a general formula (1), a general formula (4), a general formula (6) and a general formula (8) having a charge transporting ability.
Or a general formula (1), a general formula (4), a general formula (6), and a general formula (8) having a charge transporting ability.
Or a copolymerized polycarbonate resin comprising a structural unit represented by the general formula (2) as a structural unit for imparting a property other than the charge transporting ability, or a general formula (3) having a charge transporting ability. , The general formula (5),
An alternating copolymer polycarbonate resin comprising the repeating units represented by the general formula (7) and the general formula (9). These aromatic polycarbonate resins have charge transporting ability and high mechanical strength, and have the electrical, optical, and mechanical properties required for the charge transport layer of an electrophotographic photosensitive member. It is a thing.

The method for producing the aromatic polycarbonate resin of the present invention will be described below.

The polycarbonate resin of the present invention can be 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. That is, the following general formulas (10), (11), (12),
At least one diol having a charge transporting ability represented by (13) is used, and it is derived from a transesterification method with a bisaryl carbonate, a solution with a carbonyl halide compound such as phosgene or an interfacial polymerization method, or a diol. It is produced by a method using a chloroformate such as bischloroformate. As the carbonyl halide compound, instead of phosgene, trichloromethylchloroformate which is a dimer of phosgene and bis (trichloromethyl) carbonate which is a trimer of phosgene are also useful, and halogens derived from halogens other than chlorine are also useful. Also useful are carbonyl iodide compounds such as carbonyl bromide, carbonyl iodide, carbonyl fluoride. These known production methods are described in, for example, a polycarbonate resin handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun). In addition, the general formulas (10), (11), (1)
2) Use of a diol represented by the following general formula (14) in combination with one or more diols having a charge transporting ability represented by (13), and a copolymer having improved mechanical properties and the like. can do. In this case, one or more diols represented by the general formula (14) may be used in combination. The ratio of the diol having the charge transporting ability represented by the general formulas (10), (11), (12), and (13) to the diol represented by the general formula (14) is selected from a wide range depending on desired characteristics. can do. Further, by selecting an appropriate polymerization operation, a random copolymer, an alternating copolymer, a block copolymer, a random alternating copolymer, a random block copolymer and the like can be obtained among the copolymers. For example,
Condensation with phosgene by uniformly mixing the diol having the charge transporting ability represented by the general formulas (10), (11), (12) and (13) with the diol represented by the general formula (14) from the beginning When the reaction is carried out, a random copolymer comprising the structural unit represented by the general formula (1), (4), (6), or (8) and the structural unit represented by the general formula (2) is obtained. Also, a random block copolymer can be obtained by adding some kinds of diols in the middle of the reaction. Further, bischloroformate derived from the diol represented by the general formula (14) and the bischloroformate represented by the general formulas (10) and (1)
When a condensation reaction with a diol having a charge transporting ability represented by 1), (12), or (13) is carried out, general formula (3):
An alternating copolymer comprising the repeating units represented by (5), (7) and (9) is obtained. In this case, conversely, the general formula (1)
0), (11), (12), and (13) by the condensation reaction of bischloroformate derived from a diol having a charge transporting ability and a diol represented by the general formula (14). The general formulas (3), (5), (7),
An alternating copolymer comprising the repeating unit represented by (9) is obtained. In addition, in the condensation reaction of these bischloroformate and diol, a random alternating copolymer can be obtained by using a plurality of bischloroformate and diol.

[0035]

Embedded image

(Wherein R ¹ , R ¹⁹ , R ²⁰ , R ²¹ , A
r ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and X are the same as defined above. In the interfacial polymerization, the reaction is carried out between two phases of an alkali aqueous solution of a diol and an organic solvent that is substantially insoluble in water and dissolves polycarbonate 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 is usually sodium hydroxide, potassium hydroxide, a hydroxide such as calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate,
And carbonates such as 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. Organic solvents, for example, dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, aliphatic halogenated hydrocarbons such as dichloropropane, chlorobenzene, aromatic halogenated hydrocarbons such as dichlorobenzene, or , Their mixtures. 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 can be added before and / or after adding a carbonic acid derivative such as phosgene or bischloroformate to the reaction system.

It is desirable to use a terminal terminator as a molecular weight regulator to control the molecular weight in all of 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-
Phenols such as (2 ', 4', 4'-trimethylchromanyl) phenol and 2- (4'-methoxyphenyl) -2- (4 "-hydroxyphenyl) propane or their alkali metal salts and alkaline earths The haloformate derivative of the monovalent aromatic hydroxy compound is the above-mentioned haloformate derivative of the monovalent aromatic hydroxy compound.

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 50,000 in terms of polystyrene equivalent number average molecular weight.
0, 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 (chlorocarbonyl Oxy)
Benzoic acid, 4-hydroxyisophthalic acid, 4-chlorocarbonyloxyisophthalic acid, 5-hydroxyphthalic acid, 5-chlorocarbonyloxyphthalic acid, trimesic acid trichloride, 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 diol 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 the solution polymerization, it is obtained by dissolving a diol 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 0 to 40 ° C, and the reaction time is several minutes to
5 hours.

It is also produced by a transesterification method. In this case, the diol and the bisaryl carbonate are mixed in the presence of an inert gas, and usually mixed under a reduced pressure of 120 to 350.
React at ° 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, phenyl-
Examples thereof include p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.

The polycarbonate resin obtained as described above removes catalysts and antioxidants used during the polymerization, unreacted diols and terminal stoppers, and impurities such as inorganic salts generated during the polymerization. Used as For these purification operations, conventionally known methods described in the aforementioned polycarbonate resin handbook (editor: Seiichi Homma, published by Nippon 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 general formula (1), which is a main structural unit of the present invention, will be described in more detail with reference to specific examples.

The substituted or unsubstituted alkyl group for R ¹ , R ¹⁹ , R ²⁰ and R ²¹ is a linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups further include a halogen atom, It may contain a phenyl group or a phenyl group substituted with a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n
-Butyl group, i-butyl group, trifluoromethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like.

Examples of the substituted or unsubstituted aryl group for R ¹ and Ar ³ include a phenyl group, which may have the above-mentioned substituted or unsubstituted alkyl group as a substituent. Specific examples include a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group.

The substituted or unsubstituted arylene group for Ar ¹ , Ar ² , Ar ⁴ and Ar ^{5 includes} a divalent group derived from the substituted or unsubstituted aryl group defined for R ¹ and Ar ^3. Can be.

The structural units of the general formula (1) have been described above, but the same symbols have the same definitions in other general formulas.

The aromatic polycarbonate resin of the present invention comprises a polycarbonate resin having only the constitutional unit represented by the above general formula (1) having a charge transporting ability and a constitutional unit comprising the constitutional unit and other constitutional units for controlling mechanical properties. It is a copolymer. As other structural units, conventionally known structural units of a polycarbonate resin can be used as they are. For example, a basic unit described in a polycarbonate resin handbook (editor: Seiichi Honma, published by Nippon Kogyo Shimbun) can be used. Among such conventionally known structural units, a preferable example is a structural unit represented by the general formula (2). Hereinafter, the general formula (2), which is another main structural unit, will be described in detail with reference to the example of the general formula (14) as a raw material.

When X in the general formula (14) is an aliphatic divalent group or a cycloaliphatic divalent group, typical examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and poly (ethylene glycol). Tetramethylene 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 divalent groups derived from substituted or unsubstituted aryl groups defined for R ¹ and Ar ³ . X represents a divalent group shown below.

[0056]

Embedded image

(Where R ² , R ³ , R ⁴ and R ⁵ 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]

Embedded image

Wherein Y ¹ and Y 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 ² and R ^3, 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; Of these, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group each represent R ¹ , R ¹⁹ ,
It is the same as the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group defined for R ²⁰ , R ²¹ and Ar ³ . Further, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. When Y ¹ and Y ² are a substituted or unsubstituted aliphatic divalent group, the hydroxyl group is removed from the diol when X is an aliphatic divalent group or a cycloaliphatic divalent group. Divalent groups can be mentioned.
Further, when Y ¹ and Y ² are substituted or unsubstituted arylene groups, a divalent group derived from a substituted or unsubstituted aryl group defined for R ¹ , R ¹⁹ , R ²⁰ and Ar ³ may be used. Can be mentioned.

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) madamantane, 4,4'-dihydroxydiphenyl ether, 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-sioxine, 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, etc., and 2 moles of diol Also useful are aromatic diol compounds containing ester linkages produced by the reaction of 1 mole of isophthaloyl chloride or terephthaloyl chloride.

The structural unit of the general formula (2) has been described above with reference to the example of the general formula (14) as a raw material, but the same symbols have the same definitions in other general formulas.

The content of the structural unit of the general formula (1) in the copolymerized polycarbonate resin of the structural unit of the general formula (1) and the structural unit of the general formula (2) can be selected within an arbitrary range. Since the content of the structural unit represented by the general formula (1) corresponds to the charge transporting property of the polycarbonate resin, the content is preferably 5 mol% or more, more preferably 20 mol% or more in all the structural units.

[0063]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to examples. However, the present invention is not limited to these examples.

Example 1 The following formula

[0065]

Embedded image

2.92 g (5.6 mmol) of a hydroxystilbene compound represented by the following formula:
99 g (7.4 mmol), t-butylphenol 0.
050 g was placed in a reaction vessel, and 0.062 g of hydrosulfite and 2.0 g of sodium hydroxide were added under an argon gas stream.
41 ml of ion-exchanged water in which 60 g was dissolved was added and stirred. To this, 35 ml of dichloromethane in which 1.54 g of triphosgene was dissolved was added dropwise at 20 ° C., and 1 drop of triethylamine was added, followed by a reaction for 90 minutes. To this reaction solution, 0.107 g of phenyl chloroformate was added, and the mixture was further stirred for 2 hours. 200 ml of dichloromethane was added to the obtained reaction solution.
And then washed in order with a 3% aqueous sodium hydroxide solution, a 2% aqueous hydrochloric acid solution and ion-exchanged water, and then reprecipitated in methanol to give the following formula

[0067]

Embedded image

4.31 of the polycarbonate resin represented by
g (85.7% yield).

When the molecular weight of the obtained polycarbonate resin was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows.

Number average molecular weight 44500 Weight average molecular weight 90800 The glass transition temperature (Tg) was 163.8 ° C.

The elementary analysis values were as follows, as C _25.88 H _21.87 N _0.43 O ₃ .

[0072] FIG. 1 shows an infrared absorption spectrum (cast film).

Examples 2 to 5 The procedure of Example 1 was repeated, except that the starting materials, hydroxystilbene compound and copolymer, were changed to those shown in Table 1. 2 to 5 polycarbonate resins were obtained. The results are summarized in Table 2.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

Application Example 1 A solution of a polyamide resin (CM-8000: manufactured by Toray Industries, Ltd.) dissolved in a mixed solvent of methanol / butanol was applied on an aluminum plate 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.

[0078]

Embedded image

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

The photosensitive member No. 1 was charged using a commercially available electrostatic copying paper tester (SP428, manufactured by Kawaguchi Electric Works Co., Ltd.) in a dark place by performing a −6 kV corona discharge for 20 seconds.
_m (V) was measured and left in a dark place for further 20 seconds, and then 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 = −1480 V V ₀ −1269 V E _1/2 = 1.31 lux · sec Further, after charging the above-mentioned photoreceptor using a commercially available electrophotographic copying machine, light was applied through the original drawing. Irradiation was performed to form an electrostatic latent image, developed using a dry developer, and the resulting image (toner image) was electrostatically transferred onto plain paper and fixed. A clear transferred image was obtained. . Similarly, when a wet type developer was used as the developer, a clear transfer image was obtained.

[0082]

The novel aromatic polycarbonate resin according to the present invention effectively functions as a photoconductive material as described above, and is optically or chemically sensitized by a sensitizer such as a dye or Lewis acid. Is done. Further, it is suitably used as a charge transporting material in a photosensitive layer of an electrophotographic photoreceptor, and is particularly useful as a charge transporting material in a so-called function-separated type photosensitive layer in which a charge generating layer and a charge transporting layer are divided into two layers. It is.

[Brief description of the drawings]

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

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

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

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

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaomi Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Kazuki Nagai 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Shinichi Kawamura 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Li Hongkook 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 F term in reference (reference) 2H068 AA20 BB25 4J029 AA09 AB04 AB07 AC02 AC03 AE18 BB10A BB10B BB12A BB12B BB12C BB13A BB13B BB13C BB15A BD09A BD09B BE05A BE05B BE07 BF14A BF21 BF21BF 30 BG07X BG08X BG08Y BG20X BG24X BH01 BH02 BH04 DA09 DB07 DB11 DB13 FA07 FB02 FB03 FB04 FB07 HA01 HC01 HC02 HC05A JC031 JC041 JC091 JC231 JC261 JC451 JC631 KA01 KD01 KE07 KE07 KE02

Claims (12)

[Claims] 1. A polycarbonate resin containing a structural unit represented by the following general formula (1). Embedded image (In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
r ¹ , Ar ² , Ar ⁴ and Ar ⁵ represent a substituted or unsubstituted arylene group, which may be the same or different.
Ar ³ represents a substituted or unsubstituted aryl group. ) 2. The general formula (1) and the following general formula (2)
Where k is the composition ratio of the structural unit represented by the general formula (1) and j is the composition ratio of the structural unit represented by the general formula (2). Is 0 <k /
A polycarbonate resin in which (k + j) ≦ 1. Embedded image [Wherein, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or (Where R ² , R ³ , R ⁴ , and R ⁵ 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 Y ¹ and Y 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 ² and R ^3, 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. ). ] 3. A polycarbonate resin comprising a repeating unit represented by the following general formula (3). Embedded image (Wherein, R ¹ , Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , X
Is the same as the previous definition, and n is the number of repetitions 2 to 5000
Represents an integer. ) 4. A polycarbonate resin containing a structural unit represented by the following general formula (4). Embedded image (Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, R ^19,
R ²⁰ represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, which may be the same or different. Ar ³ represents a substituted or unsubstituted aryl group. ) 5. The general formula (4) and the general formula (2)
Where k is the composition ratio of the structural unit represented by the general formula (4) and j is the composition ratio of the structural unit represented by the general formula (2). Is 0 <k /
A polycarbonate resin in which (k + j) ≦ 1. 6. A polycarbonate resin containing a structural unit represented by the following general formula (5). Embedded image (Wherein, R ¹ , R ¹⁹ , R ²⁰ , Ar ³ , X, and n are the same as defined above.) 7. A polycarbonate resin comprising a repeating unit represented by the following general formula (6). Embedded image (In the formula, R ¹ , R ¹⁹ , R ²⁰ , and Ar ³ are the same as defined above.) 8. The general formula (6) and the general formula (2)
Where k is the composition ratio of the structural unit represented by the general formula (6) and j is the composition ratio of the structural unit represented by the general formula (2). Is 0 <k /
A polycarbonate resin in which (k + j) ≦ 1. 9. A polycarbonate resin containing a structural unit represented by the following general formula (7). Embedded image (Wherein, R ¹ , R ¹⁹ , R ²⁰ , Ar ³ , X, and n are the same as defined above.) 10. A polycarbonate resin comprising a repeating unit represented by the following general formula (8). Embedded image (Wherein, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, R ^19,
R ²⁰ and R ²¹ represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, and may be the same or different. ) 11. A composition comprising the structural units represented by the general formula (8) and the general formula (2), wherein the composition ratio of the structural unit represented by the general formula (8) is k and the general formula (2) When the composition ratio of the structural unit represented is j, the composition ratio is 0 <
A polycarbonate resin in which k / (k + j) ≦ 1. 12. A polycarbonate resin comprising a repeating unit represented by the following general formula (9). Embedded image (Wherein, R ¹ , R ¹⁹ , R ²⁰ , R ²¹ , X, and n are the same as defined above.)