JP3352326B2 - Aromatic polycarbonate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aromatic polycarbonate resin useful as a photoreceptor 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 a binder resin for an organic photoreceptor used in electrophotography. As a typical configuration example of an organic photoreceptor,
Examples include a laminated photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated 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 lowers 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. It 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 .; Polym. Sci. , 219
69 (1983)] and a photoconductive polymer material such as an aromatic polycarbonate resin having a benzidine structure (JP-A-64-9964) have been studied, but have not been put to practical use.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides an aromatic polycarbonate resin which is particularly useful as a charge transporting polymer material for an organic photoreceptor. Is its purpose.

[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 includes the following (1) and (2). (1) A polycarbonate resin comprising a repeating unit represented by the following general formula (III).

Embedded image [Wherein, Ar ¹ , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ represent the same or different substituted or unsubstituted arylene groups;
r ² and Ar ⁷ represent the same or different substituted or unsubstituted aryl groups; X represents an aliphatic divalent group;
Divalent group, aromatic divalent group or divalent group formed by linking these, or

Embedded image (Where R ¹ , R ² , R ³ , and R ⁴ 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 0 to 3
Y is a single bond, a linear alkylene group having 2 to 12 carbon atoms, -O-, -S-, -SO-, -SO
_2- , -CO-,

Embedded image Wherein Z ¹ and Z ² represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group;
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ 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, a substituted or unsubstituted aryl group, and R ⁵ and R ⁶ may combine to form a carbon ring or a heterocyclic ring having 5 to 12 carbon atoms; R ⁵ and R ⁶ may form a carbocyclic or heterocyclic ring together with R ¹ and R ² ;
R ¹² and R ¹³ represent a single bond or an alkylene group having 1 to 4 carbon atoms, and e represents an integer of 0 to 4. ), And n
Represents an integer of 2 to 5000 in the number of repetitions. (2) A polycarbonate resin comprising a repeating unit represented by the following general formula (V).

[0006]

[0007]

[0008]

[0009]

[0010]

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

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[Wherein, Ar ² , Ar ⁴ , Ar ⁷ , and X are the same as defined above, and n represents an integer of 2 to 5000 in the number of repetitions. ] Formula aromatic polycarbonate resin of the present invention as described above, with the electric charge transport ability (III),
An alternating copolymer polycarbonate resin comprising a repeating unit represented by the general formula (V). 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. Hereinafter, a method for producing the aromatic polycarbonate resin of the present invention will be described.

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 formula (VI), at least one or more and the following general the diol having a charge transportability represented by (VII)
Using a diol represented by the formula (VIII), a transesterification method with a bisaryl carbonate, a solution with a carbonyl halide compound such as phosgene or an interfacial polymerization method, or a chloroformate such as a bischloroformate derived from a diol And the like. As the carbonyl halide compound, instead of phosgene, phosgene dimer trichloromethylchloroformate and phosgene trimer bis (trichloromethyl)
Carbonates are also useful, and carbonyl halide compounds derived from halogens other than chlorine, such as carbonyl bromide, carbonyl iodide, and carbonyl fluoride are also useful. These known production methods are described, for example, in "Polycarbonate Resin Handbook" (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun) . One general formula (V
Use of a diol represented by the following general formula (VIII) in combination with one or more diols having charge transport ability represented by I) and (VII) to obtain a copolymer having improved mechanical properties and the like. Can be. In this case, one or more diols represented by the general formula (VIII) may be used in combination. The ratio of the diol having the charge transporting ability represented by the general formulas (VI) and (VII) to the diol represented by the general formula (VIII) can be selected from a wide range depending on desired characteristics .
One general formula (VIII) with a diol bischloroformate the general formula derived from the represented (VI), by performing the condensation reaction of a diol having a charge transportability represented by (VIII) formula (III), An alternating copolymer comprising a repeating unit represented by (V) is obtained. In this case, the general formula (V
Bischloroformates derived from diols having charge transporting ability represented by I) and (VII) and general formula (VIII)
Similarly, an alternate copolymer comprising repeating units represented by the general formulas (III) and (V) can be obtained by a condensation reaction with a diol represented by the following formula: 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.

[0021]

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HO—X—OH (VIII) [wherein Ar ^{1 to} Ar ⁷ and X in each formula are the same as defined above. In the interfacial polymerization, a 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 carbonic acid 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,
Carbonates such as sodium carbonate, potassium carbonate, calcium carbonate and sodium hydrogen carbonate. These bases may be used alone or in combination of two or more. Preferred bases are sodium or potassium hydroxide. The water used is preferably distilled water or ion-exchanged water.
Organic solvents are, for example, dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane,
It is an aliphatic halogenated hydrocarbon such as tetrachloroethane or dichloropropane, an aromatic halogenated hydrocarbon such as chlorobenzene or 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, 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 a tertiary amine, more preferably a tertiary amine having a total of 3 to 30 carbon atoms, 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.

In all of the above polymerization operations, it is desirable to use a terminal terminator as a molecular weight regulator in order to control the molecular weight. Therefore, the terminal of the polycarbonate resin used in the present invention has a substituent based on the terminator. They may be combined. 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. Monovalent aromatic hydroxy compounds include, 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-bis (1-methyl-1 -Phenylethyl) phenol, β
Phenols such as naphthol, α-naphthol, p- (2,4,4-trimethylchromanyl) phenol, 2- (4-methoxyphenyl) -2- (4-hydroxyphenyl) propane or alkali metal salts thereof And alkaline earth metal salts. The haloformate derivative of the monovalent aromatic hydroxy compound is the above-described haloformate derivative of the monovalent aromatic hydroxy compound.

Monovalent carboxylic acids include, 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
-Fatty acids such as dimethylvaleric acid, 4-methylcaproic acid, 3,5-dimethylcaproic acid, phenoxyacetic acid or alkali metal and alkaline earth metal salts thereof, benzoic acid, p-methylbenzoic acid, p-tert Benzoic acids such as -butylbenzoic acid, p-butoxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid, p-chlorobenzoic acid, and alkali metal salts and alkaline earth metals thereof; Salt. 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 terminator 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 500,000, more preferably 10,000 to 200,000 in terms of polystyrene.

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,
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, trimesic acid trichloride, cyanuric chloride and the like. These branching agents may be used alone or in combination of two or more.

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 preferably maintained at 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 or phosgene or a polymer of phosgene thereto. As a deoxidizing agent, trimethylamine,
Tertiary amines such as triethylamine, tripropylamine and pyridine are used. As the solvent used in the reaction, for example, dichloromethane, dichloroethane,
Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, trichloroethylene and chloroform, and cyclic ether solvents such as tetrahydrofuran and dioxane, and pyridine are preferred. 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 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 above-mentioned "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, general formula (III) , which is a main structural unit of the present invention, will be described in more detail. In the general formula (III) , Ar ² and Ar ⁷ represent a substituted or unsubstituted aryl group.

Specifically, examples of the aryl group include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group,
Pyrenyl group, fluorenyl group, 9,9-dimethyl-2-
Fluorenyl, azulenyl, anthryl, triphenylenyl, chrysenyl, fluorenylidenephenyl, 5H-dibenzo [a, d] cycloheptenylidenephenyl, thienyl, benzothienyl, furyl, benzofuranyl, carbazolyl Group, pyridinyl group, pyrrolidyl group, oxazolyl group, the following general formula (IX)
And the like. As these substituents, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, represented by the following general formula An amino group is mentioned. Examples of the substituted or unsubstituted alkyl group include the following. It is a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, and these alkyl groups are furthermore a fluorine atom, a cyano group, a phenyl group, a halogen atom or a
It may contain a phenyl group substituted with 5 linear or branched alkyl groups. Specifically, a methyl group, an ethyl group,
n-propyl group, iso-propyl group, tert-butyl group, sec-butyl group, n-butyl group, iso-butyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4 -Methylbenzyl group and the like. The alkyl group of the substituted or unsubstituted alkoxy group is the same as the above-defined substituted or unsubstituted alkyl group.

[0032]

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[Wherein B is -O-, -S-, -SO-,
—SO ₂ —, —CO— and the following divalent groups are selected.

[0034]

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(Wherein R ¹⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group as defined above, a substituted or unsubstituted alkoxy group, a halogen atom, a substituted or unsubstituted aryl group as defined above, R ¹⁷ represents a hydrogen atom, a substituted or unsubstituted alkyl group as defined above, a substituted or unsubstituted aryl group as defined above, and h represents 1 to 12; And i represents an integer of 1 to 3.)]

[0036]

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[Wherein R ¹⁸ and R ¹⁹ represent a substituted or unsubstituted alkyl group as defined above, or a substituted or unsubstituted aryl group as defined above, and R ¹⁸ and R ¹⁹ are a ring together. Or may form a ring together with a carbon atom on the aryl group. Specific examples of such a group include a piperidino group, a morpholino group, a julolidyl group, and the like. ]
Examples of the arylene group of Ar ¹ , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ include a divalent group derived from a substituted or unsubstituted aryl group defined in Ar ² and Ar ⁷ .
The structural units of the general formula (III) have been described above, but the same symbols have the same definitions in other general formulas.

The aromatic polycarbonate resin of the present invention are copolymers of other building blocks for adjusting the configuration unit and mechanical properties that have a charge transportability. Below it
This will be described in detail with reference to examples of the general formula (VIII), which is a raw material of a structural unit other than the above.

When X in the formula (VIII) is an aliphatic divalent group or a cycloaliphatic divalent group, typical specific examples of diols 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 and the like. Examples of the case where X is an aromatic divalent group include a divalent group derived from a substituted or unsubstituted aryl group defined by Ar ² and Ar ⁷ .
X represents a divalent group shown below.

[0040]

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(Where R ¹ , R ² , R ³ and R ⁴ 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-,

[0042]

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And Z ¹ and Z ^{2 each} represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ 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, or a substituted or unsubstituted aryl group; And R ⁵ and R ⁶ are bonded to each other to have 5 carbon atoms.
To 12 carbocycles or heterocycles;
⁵ , R ⁶ may form a carbocyclic or heterocyclic ring together with R ¹ and R ² , R ¹² and R ^{13 each} represent a single bond or an alkylene group having 1 to 4 carbon atoms , and e represents 0 to Represents an integer of 4 . ) In these, the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group are the same as the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group defined above. The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Also, Z
Examples of the case where ¹ and Z ² are a substituted or unsubstituted aliphatic divalent group include divalent groups obtained by removing a hydroxyl group from a diol when X is an aliphatic divalent group or a cycloaliphatic divalent group. Groups. 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 Ar ² and Ar ⁷ .

Representative 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′-dihydroxydiphenylsphone, 3,3′-dimethyl-4,
4'-dihydroxydiphenylsphone, 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, , 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-dihydroxydibenzo-p-dioxane, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxatiin, 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- Examples include bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, and phenol-modified silicone oil. Also useful are aromatic diols containing ester linkages produced by the reaction of 2 moles of diol with 1 mole of isophthaloyl chloride or terephthaloyl chloride.

The same definition der even during other formulas have been described by way of example than on one general formula (VIII) for the same symbol
You.

[0046]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to examples. In the following examples, all parts are parts by weight. Example 1 A diol compound having a tertiary amino group having the following structure was used as a starting material.

[0047]

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1,4-Bis @ 4- in 50 ml of dry THF
[N-phenyl-N- (4-hydroxyphenyl) amino] styryl @ benzene 6.48 g (0.01 mol)
l), 3.04 g (0.03 mol) of triethylamine
Was dissolved. To this solution was added 2.31 g (0.01 mol) of diethylene glycol bischloroformate in dry T
What was dissolved in 8 ml of HF was added dropwise over 30 minutes under water cooling. After the dropwise addition, the viscous mixture was further stirred for 15 minutes, and a solution prepared by dissolving 0.1 g of phenol in 5 ml of dry THF was added. After stirring for 5 minutes, the resulting viscous mixture was precipitated in methanol and the crude product was collected by filtration. This was treated with methylene chloride dissolution-methanol precipitation for 2 minutes.
The precipitate was collected by filtration and dried to obtain a polycarbonate resin No. 1) having the following structural formula. The obtained target was 6.6.
The yield was 82.0% in 1 g. The glass transition point of this product was 142 ° C.

[0049]

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When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Number average molecular weight 41100 Weight average molecular weight 177300 The infrared absorption spectrum (film) of this product is shown in FIG. 1, and absorption based on C = O stretching vibration of carbonate was observed at 1760 cm ^-1 . Table 1 shows the results of elemental analysis.
Shown in

[0051]

[Table 1]

Example 2 The same diol having a tertiary amino group as in Example 1 was used as a starting material. 6.48 g (0.01) of 1,4-bis {4- [N-phenyl-N- (4-hydroxyphenyl) amino] styryl} benzene is added to 50 ml of dry THF.
mol), 3.04 g of triethylamine (0.03 mol
l) was dissolved. To this solution was added polytetramethylene ether glycol bischloroformate (average molecular weight 25
0 from polytetramethylene ether glycol)
A solution obtained by dissolving 3.79 g (0.01 mol) in dry THF (8 ml) was added dropwise over 30 minutes while cooling with water. After completion of the dropwise addition, the viscous mixture was further stirred for 15 minutes, and a solution prepared by dissolving 0.1 g of phenol in 5 ml of dry THF was added.
After drying for 5 minutes, the resulting viscous mixture was precipitated in methanol, and the crude product was collected by filtration. This was treated twice with THF dissolution and methanol precipitation, and the precipitate was collected by filtration and dried to obtain a polycarbonate resin (No. 2) having the following structural formula. The obtained target substance was 8.28 g and the yield was 86.8.
%Met.

[0053]

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When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Number average molecular weight 40400 Weight average molecular weight 107000 The glass transition point is 86 ° C., and the infrared absorption spectrum (film) of this product is shown in FIG. 2. The absorption at 1760 cm ⁻¹ based on the C = 0 stretching vibration of carbonate is shown. Admitted. Table 2 shows the results of elemental analysis.

[0055]

[Table 2]

Examples 3 to 10 By operating in the same manner as in Example 1, the aromatic polycarbonate resins of the present invention shown in the following table were obtained. The basic structures of the compounds of Examples 3 to 4 and 6 to 10 are represented by the following general formula.

[0057]

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The structure of the compound of Example 5 is represented by the following formula.

[0059]

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Table 3 shows the results.

[0061]

[Table 3]

Application Example 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. A dispersion obtained by pulverizing and dispersing a bisazo compound represented by the following formula with cyclohexanone as a charge generating substance was applied thereon by a doctor blade, and naturally dried to form a charge generating layer of about 1 μm.

[0063]

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Next, 1 part of the polycarbonate resin No. 1 obtained in Example 1 was mixed and dissolved in 9 parts of methylene dichloride as a charge transporting substance, and this solution was applied on the charge generating layer with a doctor blade and air-dried. And then 12
After drying at 0 ° C. for 20 minutes, a charge transport layer having a thickness of about 20 μm was formed to prepare a photoreceptor. The photoreceptor thus produced was charged by performing a −6 kV corona discharge for 20 seconds in a dark place using a commercially available electrostatic copying paper tester (SP428, manufactured by Kawaguchi Electric Works), and then charged. The surface potential V _m (V) was measured, and after standing in a dark place for further 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, and a time (second) until V ₀ becomes 1/2.
Was calculated, and the exposure amount E _1/2 (lux · sec) was calculated.
As a _{result, V o = -737 (V)} , E 1/2 = 0.76 (l
ux · sec).

After charging the above photoreceptor using a commercially available electrophotographic copying machine, it is irradiated with light through the original drawing to form an electrostatic latent image, and is developed using a dry developer.
The obtained image (toner image) is electrostatically transferred onto plain paper,
Upon fixing, a clear transferred image was obtained. Similarly, when a wet type developer was used as the developer, a clear transfer image was obtained.

[0066]

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 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 is an infrared absorption spectrum of a compound of Example 1 of the present invention.

FIG. 2 is an infrared absorption spectrum of the compound of Example 2 of the present invention.

FIG. 3 is an infrared absorption spectrum of the compound of Example 3 of the present invention.

FIG. 4 is an infrared absorption spectrum of the compound of Example 4 of the present invention.

FIG. 5 is an infrared absorption spectrum of the compound of Example 5 of the present invention.

FIG. 6 is an infrared absorption spectrum of the compound of Example 6 of the present invention.

FIG. 7 is an infrared absorption spectrum of the compound of Example 7 of the present invention.

FIG. 8 is an infrared absorption spectrum of the compound of Example 8 of the present invention.

FIG. 9 is an infrared absorption spectrum of the compound of Example 9 of the present invention.

FIG. 10 is an infrared absorption spectrum of the compound of Example 10 of the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Masaomi Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Masafumi Ota 1-3-6 Nakamagome, Ota-ku, Tokyo Co., Ltd. (72) Inventor Tamotsu Ariga 1-3-6 Nakamagome, Ota-ku, Tokyo Co., Ltd. Ricoh Co., Ltd. (72) Inventor Kazuki Nagai 1-3-6 Nakamagome, Ota-ku, Tokyo Co., Ltd. Ricoh Co., Ltd. (56) References JP-A-5-230202 (JP, A) JP-A-8-62864 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY (STN) WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. A polycarbonate resin comprising a repeating unit represented by the following general formula (III). Embedded image [Wherein, Ar ¹ , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ represent the same or different substituted or unsubstituted arylene groups;
r ² and Ar ⁷ represent the same or different substituted or unsubstituted aryl groups; X represents an aliphatic divalent group;
A divalent group, an aromatic divalent group or a divalent group formed by linking these, or (Where R ¹ , R ² , R ³ , and R ⁴ 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 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;
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ 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, a substituted or unsubstituted aryl group, and R ⁵ and R ⁶ may combine to form a carbon ring or a heterocyclic ring having 5 to 12 carbon atoms; R ⁵ and R ⁶ may form a carbocyclic or heterocyclic ring together with R ¹ and R ² ;
R ¹² and R ¹³ represent a single bond or an alkylene group having 1 to 4 carbon atoms, and e represents an integer of 0 to 4. ), And n
Represents an integer of 2 to 5000 in the number of repetitions. ] 2. A polycarbonate resin comprising a repeating unit represented by the following general formula (V). Embedded image (In the formula, Ar ² , Ar ⁴ , Ar ⁷ , and X are the same as defined above, and n represents an integer of 2 to 5000 in the number of repetitions.)