JPH09272735A - Aromatic polycarbonate resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic polycarbonate resin having charge transport capacity and high mechanical strengths and being useful as a photoconductive material by selecting a resin comprising specified structural units. SOLUTION: This resin comprises structural units represented by formula I [wherein Ar<1> is a (substituted) aryl; R<1> is H, a (substituted) alkyl or Ar<1> ; and Ar<2> and Ar<3> are each a (substituted) arylene]. Alternatively, it comprises structural units represented by formula I and structural units represented by formula II X is a divalent (cyclo)aliphatic, aromatic or (cyclo)aliphatic-aromatic group or a group represented by formula III or IV [R<2> to R<5> are each Ar<1> , a (substituted) alkyl or a halogen; a and b are each 0-4: c and d are each 0-3; and Y is a single bond, a 2-12C linear alkylene, O, S, SO, SO2 , CO or the like]} in amounts satisfying the relationships: 0<k/(k+j)<1 (k is the compositional ratio of the structural units represented by formula I, and j is that of the structural units represented by formula II).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) with phosgene or diphenyl carbonate is known as a typical one. Such polycarbonate resin from bisphenol A has excellent properties in terms of transparency, heat resistance, dimensional accuracy and mechanical strength, and is therefore used in many fields. As one example thereof, various studies have been made as a binder resin for an organic photoconductor used in electrophotography. As a typical configuration example of the organic photoreceptor, there is 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 many aromatic polycarbonate resins have been proposed as the binder resin. However, the inclusion of the low-molecular charge transport material reduces the mechanical strength originally possessed by the binder resin, which causes deterioration of the photoconductor's wear properties, scratches, cracks, etc., and impairs the durability of the photoconductor. Has become.

On the other hand, an acrylic resin having polyvinyl anthracene, polyvinyl pyrene, poly-N-vinyl carbazole and triphenylamine as a side chain [M. Stolka et.
al, J. Polym, Sci., 21, 969 (1983)] and an aromatic polycarbonate resin having a benzidine structure (Japanese Patent Application Laid-Open No. 6-58242).
Although a photoconductive polymer material such as JP-A-4-9964) has been studied, it 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 family for organic photoreceptors. The purpose is to do.

[0005]

As a result of intensive studies, the present inventors have found that a novel aromatic polycarbonate resin containing a specific constitutional unit can solve the above problems, and have completed the present invention. . That is, according to the present invention, the following aromatic polycarbonate resins (1) to (9) are provided. (1) An aromatic polycarbonate resin containing a structural unit represented by the following general formula (I).

Embedded image (In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹
Represents a substituted or unsubstituted aryl group, and Ar ² , A
r ³ represents a substituted or unsubstituted arylene group. (2) The composition ratio of the structural unit represented by the general formula (I) and the following general formula (II) is represented by k, and the compositional ratio of the structural unit represented by the general formula (I) is represented by k. The composition ratio is 0 <k / (k + j), where j is the composition ratio of the constituent units.
An aromatic polycarbonate resin with ≦ 1.

Embedded image (In the formula, R ¹ , Ar ¹ , Ar ² and Ar ³ are the same as defined above.)

Embedded image (In the formula, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or

Embedded image (Here, 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 0.
Is an integer of 4 to 4, 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- or the following formula

Embedded image Z ¹ and Z ² represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R 1
⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a C 1 to 5 carbon atom. It represents a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and R ⁶ and R ⁷ may combine with each other to form a carbocycle or heterocycle having 5 to 12 carbon atoms. ⁶ , R ⁷ may form a carbocycle or a heterocycle together with R ² and R ³ , R ¹³ and R ¹⁴ represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ Each independently represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, e is an integer of 0 to 4, and f is 0 to 20.
, And g represents an integer of 0 to 2000. ) Represents a group selected from. (3) An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (III).

Embedded image (In the formula, R ¹ , Ar ¹ , Ar ² , Ar ³ and X are the same as defined above, and n represents the degree of polymerization and represents an integer of 2 to 5000.) (4) In the following general formula (IV) An aromatic polycarbonate resin containing the structural unit represented.

[Chemical 6] (In the formula, Ar ² and Ar ³ are the same as defined above, and Ar ⁴
Represents a substituted or unsubstituted arylene group. R ¹⁷ , R ¹⁸
Represent the same or different acyl groups, substituted or unsubstituted alkyl groups, and substituted or unsubstituted aryl groups. (5) Constituting the constitutional unit represented by the following general formula (IV) and the following general formula (II), the composition ratio of the constitutional unit represented by the general formula (IV) is represented by k, and is represented by the general formula (II). The composition ratio is 0 <k / (k + j), where j is the composition ratio of the constituent units.
An aromatic polycarbonate resin with ≦ 1.

[Chemical 6] (In the formula, R ¹⁷ , R ¹⁸ , Ar ² , Ar ³ and Ar ⁴ are the same as defined above.)

Embedded image (In the formula, X is the same as the above definition.) (6) An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (V).

Embedded image (In the formula, R ¹⁷ , R ¹⁸ , Ar ² , Ar ³ , Ar ⁴ and X are the same as defined above, and n represents the degree of polymerization and represents an integer of 2 to 5000.) (7) The following general formula ( An aromatic polycarbonate resin containing a structural unit represented by VI).

Embedded image (In the formula, R ¹⁷ and R ¹⁸ are the same as defined above.) (8) Consists of structural units represented by the following general formula (VI) and the following general formula (II), represented by the general formula (VI). When the composition ratio of the constituent unit is k and the composition ratio of the constituent unit represented by the general formula (II) is j, the composition ratio is 0 <k / (k + j).
An aromatic polycarbonate resin with ≦ 1.

Embedded image (In the formula, R ¹⁷ and R ¹⁸ are the same as defined above.)

Embedded image (In the formula, X is the same as the above definition.) (9) An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (VII).

Embedded image (In the formula, R ¹⁷ , R ¹⁸ , and X are the same as defined above, and n is a degree of polymerization and represents an integer of 2 to 5000.)

As described above, the aromatic polycarbonate resin of the present invention contains at least the constitutional unit represented by the general formula (I), the general formula (IV) and the general formula (VI) having a charge transporting ability. Polycarbonate resin, which has the above-mentioned general formula (I) and general formula (IV) and has charge transporting ability.
And a polycarbonate resin composed of only the structural unit represented by the general formula (VI), or the general formula (I), the general formula (IV) and the general formula (VI) having a charge transporting ability.
A copolymerized polycarbonate resin comprising a structural unit represented by the general formula (II) as a structural unit for imparting properties other than charge transporting ability, or a general formula having a charge transporting ability ( III), an alternating copolymer polycarbonate resin comprising repeating units represented by the general formula (V) and the general formula (VII). These aromatic polycarbonate resins have charge transporting ability and high mechanical strength, and combine electrical properties, optical properties and mechanical properties required for the charge transport layer of an electrophotographic photoreceptor. I have it.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic polycarbonate resin of the present invention will be described in detail below. First, the method for producing the polycarbonate resin of the present invention will be described. The polycarbonate resin of the present invention can be produced by the same method as the polymerization of bisphenol and a carbonic acid derivative, which is conventionally known as a method for producing a polycarbonate resin. That is, at least one diol having charge transfer ability represented by the following general formulas (VIII), (IX) and (X) is used, or
By combining these with a diol represented by the following general formula (XI), a method of transesterification with a bisaryl carbonate, a solution or an interfacial polymerization with a carbonyl halide compound such as phosgene, or a bischloro derivative derived from a diol It is produced by a method using chloroformate such as formate.

Embedded image

Embedded image

Embedded image

HO-X-OH (XI) (R ¹ , R ¹⁷ , R ¹⁸ , Ar ¹ , Ar ² , Ar ³ , A in each formula)
r ⁴ and X are the same as defined above. )

In the method using the above-mentioned carbonyl halide compound, the carbonyl halide compound may be, instead of phosgene, trichloromethylchloroformate which is a dimer of phosgene or bis (trichloromethyl) which is a trimer of phosgene. Carbonates are also useful,
Also useful are carbonyl halide compounds derived from halogens other than chlorine, such as carbonyl bromide, carbonyl iodide, carbonyl fluoride. These known production methods are described in, for example, the Polycarbonate Resin Handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun).

As described above, the general formulas (VIII) and (I
X), a diol 1 having charge transfer ability represented by (X)
By using the diol represented by the general formula (XI) in combination with one or more species, a copolymer having improved mechanical properties and the like can be obtained. In this case, one or more diols represented by formula (XI) may be used in combination. General formula (VII
The ratio of the diol having the charge transporting ability represented by I), (IX) and (X) to the diol represented by the general formula (XI) can be selected from a wide range depending on the desired characteristics.
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, the general formula (VIII),
If the diol having the charge-transporting ability represented by (IX) or (X) and the diol represented by the general formula (XI) are uniformly mixed from the beginning to carry out the condensation reaction with phosgene, the compound represented by the general formula (I) or A random copolymer comprising a structural unit represented by (IV) or (VI) and a structural unit represented by the general formula (II) 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 (XI) and the general formulas (VIII), (IX),
By carrying out a condensation reaction with a diol having a charge transfer ability represented by (X), an alternating copolymer comprising repeating units represented by the general formulas (III), (V) and (VII) can be obtained. In this case, conversely, condensation of a bischloroformate derived from a diol represented by the general formulas (VIII), (IX) and (X) and having a charge transporting ability with a diol represented by the general formula (XI) Similarly, depending on the reaction, general formulas (III), (V), (VII)
An alternating copolymer comprising a repeating unit represented by 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.

In the method using a carbonyl halide compound or a chloroformate, when the interfacial polymerization is carried out, an organic solvent which is substantially insoluble in an alkaline aqueous solution of diol and water and which dissolves the polycarbonate resin. The reaction is carried out in the presence of a carbonic acid derivative and a catalyst between the two phases. At this time, a polycarbonate resin 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 alkaline aqueous solution is an alkali metal or an alkaline earth metal, and is usually a hydroxide such as sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogencarbonate or the like. Carbonate and the like. These bases may be used alone or in combination. The preferred base is sodium hydroxide or potassium hydroxide. The water used is preferably distilled water or ion-exchanged water.
The organic solvent is, for example, an aliphatic halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane or dichloropropane, an aromatic halogenated hydrocarbon such as chlorobenzene or dichlorobenzene, or , A mixture of them. Further, an organic solvent obtained by mixing them with an aromatic hydrocarbon such as toluene, xylene or ethylbenzene, or an aliphatic hydrocarbon such as hexane or cyclohexane may be used. 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 the polycarbonate resin is a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt, a nitrogen-containing heterocyclic compound and its salt, an imino ether and its salt, Examples thereof include compounds having an amide group. Specific examples of the polycarbonate generation catalyst include trimethylamine, triethylamine, tri-n-propylamine, tri-n-hexylamine, N, N, N ', N'-tetramethyl-1,4.
-Tetramethylenediamine, 4-pyrrolidinopyridine,
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
-Such as tetramethylpyrazine. The polycarbonate production catalyst is preferably a tertiary amine, more preferably a tertiary amine having a total carbon number of 3 to 30, and particularly preferably triethylamine. These polycarbonate-forming catalysts may be used alone or in combination. These catalysts can be added before and / or after adding a carbonic acid derivative such as phosgene or a bischloroformate to the reaction system.

Further, an antioxidant such as hydrosulfite may be added to prevent the oxidation of the diol in the alkaline aqueous solution. The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually preferably kept at 10 or higher.

On the other hand, when the solution polymerization is carried out, it can be obtained by dissolving a diol in a solvent, adding a deoxidizing agent, and adding bischloroformate or phosgene or a phosgene multimer thereto. As deoxidizing agents, tertiary amines such as trimethylamine, triethylamine, tripropylamine and pyridine are used. 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.
The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

It can also be produced by the transesterification method. In this case, the diol and the bisaryl carbonate are mixed in the presence of an inert gas, and usually 120 to 350 under reduced pressure.
React at ° C. The degree of reduced pressure is changed stepwise, and finally the phenols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours.
Moreover, you may add antioxidant as needed. Examples of the bisaryl carbonate include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate and the like.

In all the above-mentioned polymerization operations, it is desirable to use a terminal stopper as a molecular weight regulator to control the molecular weight. Therefore, a substituent based on the terminator is bonded to the terminal of the polycarbonate resin used in the present invention. You may. The terminating agent used is a monovalent aromatic hydroxy compound, a monovalent aromatic hydroxy compound haloformate derivative, a monovalent carboxylic acid, or a monovalent carboxylic acid halide derivative. 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-isobropenylphenol,
2,4-di (1'-methyl-1'-phenylethyl) phenol, β-naphthol, α-naphthol, p-
Phenols such as (2 ′, 4 ′, 4′-trimethylchromanyl) phenol, 2- (4′-methoxyphenyl) -2- (4 ″ -hydroxyphenyl) propane or their alkali metal salts and alkaline earths The haloformate derivative of a monovalent aromatic hydroxy compound is the haloformate derivative of a monovalent aromatic hydroxy compound described above.

Further, 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-dimethylvaleric acid, 4-methylcaproic acid,
Fatty acids such as 3,5-dimethylcaproic acid and phenoxyacetic acid, or their alkali metal salts and alkaline earth metal salts, benzoic acid, p-methylbenzoic acid, p-tert.
Benzoic acid such as -butylbenzoic acid, p-butoxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid, p-chlorobenzoic acid or their alkali metal salts and alkaline earth metals It is salt. The monovalent carboxylic acid halide derivative is, for example, the above monovalent carboxylic acid halide derivative. These terminal blocking agents may be used alone or in combination. The terminal blocking agent is preferably a monovalent aromatic hydroxy compound, more preferably phenol or p-.
It is tert-butylphenol or p-cumylphenol.

It is also possible to add a small amount of a branching agent 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 (chloro) Carbonyloxy) benzoic acid, 4-hydroxyisophthalic acid, 4-chlorocarbonyloxyisophthalic acid, 5-hydroxyphthalic acid, 5-chlorocarbonyloxyphthalic acid, trimesic acid trichloride, cyanuric acid chloride and the like.
These branching agents may be used alone or in combination.

The polycarbonate resin thus obtained removes impurities such as catalysts and antioxidants used during polymerization, unreacted diols and terminal terminators, and inorganic salts generated during polymerization. Then used. 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. The preferred molecular weight of the aromatic polycarbonate resin of the present invention is 1,000 to 500,000, more preferably 10,000 to 200,000 in terms of polystyrene equivalent number average molecular weight. In addition, the aromatic polycarbonate resin produced according to the above methods, if necessary, an antioxidant, a light stabilizer, a heat stabilizer,
Additives such as lubricants and plasticizers can be added.

Next, the repeating unit represented by the general formula (I), which is the main constituent unit of the aromatic polycarbonate resin of the present invention, will be described in more detail. In addition, in the present invention, "aryl" represents a group including a heterocyclic group.
In the general formula (I), R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted alkyl group for R ¹ include the following. It is a linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups are further a fluorine atom, a cyano group, a phenyl group or a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. It may contain a substituted phenyl group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group,
Examples thereof include i-butyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like.

Examples of the substituted or unsubstituted aryl group represented by R ¹ include the following. Phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 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 , A carbazolyl group, a pyridinyl group, a pyrrolidyl group, an oxazolyl group, and the like. These are the substituted or unsubstituted alkyl groups described above, an alkoxy group having the above substituted or unsubstituted alkyl group, and a fluorine atom, a chlorine atom, It may have a halogen atom such as a bromine atom or an iodine atom, or an amino group represented by the following general formula as a substituent.

Embedded image (Wherein, R ^19, R ²⁰ is a substituted or unsubstituted alkyl group as defined R ^1, the ring R ¹⁹ and R ²⁰ are jointly with a substituted or unsubstituted aryl group as defined for R ¹ It may be formed or may form a ring in cooperation with the carbon atom on the aryl group. Specific examples thereof include a piperidino group, a morpholino group and a julolidyl group.)

In the above general formula (I), Ar ¹ represents a substituted or unsubstituted aryl group. The substituted or unsubstituted aryl group for Ar ¹ includes a group represented by the following general formula (XII) and pyrrole, pyrazole, imidazole, triazole, dioxazole, indole, isoindole, benzimidazole, benzotriazole, benzisoxyl. Examples thereof include monovalent groups derived from a heterocyclic group having an amine structure such as sazin, carbazole, and phenoxazine. These may have a substituted or unsubstituted alkyl group defined by R ¹ , a substituted or unsubstituted aryl group, and a fluorine atom, a chlorine atom, a bromine atom or an iodine atom as a substituent.

Embedded image (In the formula, R ¹⁷ and R ¹⁸ represent an acyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Ar ⁴ represents an arylene group. h represents an integer of 1 to 3. )

In the above general formula (XII), R ¹⁷ , R ¹⁸
Examples of the acyl group include an acetyl group, a propionyl group, a benzoyl group and the like. Examples of the substituted or unsubstituted alkyl group for R ¹⁷ and R ¹⁸ include the same as the substituted or unsubstituted alkyl group defined for R ¹ . R ¹⁷ ,
Examples of the substituted or unsubstituted aryl group for R ¹⁸ include the group represented by the following general formula (XIII) in addition to the substituted or unsubstituted aryl group defined for R ¹ .

Embedded image Wherein, B is -O -, - S -, - SO -, - SO 2 -,
It is selected from —CO— and the following divalent groups.

Embedded image (Wherein, R ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group defined in R ^1, an alkoxy group, a halogen atom, a substituted or unsubstituted aryl group defined in R ^1, an amino group, a nitro group , a cyano group, R ²² is a hydrogen atom, a substituted or unsubstituted alkyl group defined in R ^1, represents a defined substituted or unsubstituted aryl group R ^1, i is an integer from 1 to 12 , J represents an integer of 1 to 3.)] Specific examples of the alkoxy group for R ²¹ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, and s. Examples include -butoxy group, t-butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group and trifluoromethoxy group. The halogen atom of R ²¹ is a fluorine atom, a chlorine atom, a bromine atom,
And iodine atoms. The amino group of R ²¹ is R ¹
Represents an amino group defined as a substituent of the substituted or unsubstituted aryl group of. Further, in the above general formula (XII), the arylene group of Ar ^{4 includes} a divalent group derived from the substituted or unsubstituted aryl group defined by R ¹ .

In the general formula (I), Ar ² and Ar ³ represent a substituted or unsubstituted arylene group. Examples of the arylene group of Ar ² and Ar ³ include a divalent group derived from the substituted or unsubstituted aryl group defined by R ¹ . Although the structural unit of the general formula (I) has been described above, the same symbols have the same definitions in other general formulas.

The above-mentioned general formulas (VIII), (IX), which are raw material monomers of the novel aromatic polycarbonate resin of the present invention,
The diol represented by (X) is also a novel compound, and these compounds, for example, the diol represented by the general formula (VIII) are represented by the following general formula (XIV) as shown in the synthetic scheme of the following Table 1. And a general formula (X
V) and a carbonyl compound represented by the following general formula (XV
It can be prepared by obtaining the stilbene compound represented by I) and then cleaving the ether or ester group.

[Table 1] [Here, R ²³ and R ²⁴ represent a substituted or unsubstituted alkyl group having the same definition as R ¹ and an acyl group having the same definition as R ¹⁷ and R ¹⁸ . R ²⁵ represents a lower alkyl group, and is specifically a linear or branched alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group,
Examples thereof include i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group and n-pentyl group. R ¹ , Ar ¹ , Ar ² and Ar ³ are the same as defined above. ]

Further, the diols represented by the above general formulas (IX) and (X) are prepared from the corresponding phosphonate and the corresponding carbonyl compound in the same manner as in the case of the diol represented by the general formula (VIII). Can be manufactured in.

The aromatic polycarbonate resin of the present invention is an aromatic polycarbonate resin consisting only of the constitutional unit of the general formula (I) having a charge transporting ability, and other constitutional units and other constitutions for adjusting mechanical properties. It is a copolymer having units. As other structural units, conventionally known structural units of a polycarbonate resin can be used as they are. For example, the basic units described in the polycarbonate resin handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun) can be used. Among such conventionally known constitutional units, the constitutional unit represented by the general formula (II) can be mentioned as a preferred example. Below is another main structural unit, the general formula (I
I) will be described in detail with reference to the example of the general formula (XI) as the raw material.

Typical examples of the diol when X in the general formula (XI) is an aliphatic divalent group or a cycloaliphatic divalent group are ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, poly 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, xylylenediol, 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.

When X is an aromatic divalent group, a divalent group derived from a substituted or unsubstituted aryl group defined by R ¹ can be mentioned. Also,
X represents a divalent group formed by connecting these divalent groups or a divalent group shown below.

Embedded image [Wherein 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 0 to 0].
Is an integer of 4, 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- or the following formula

Embedded image (Here, Z ¹ and Z ² are substituted or unsubstituted aliphatic 2
Represents a valent group or a substituted or unsubstituted arylene group,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and R ⁶ and R ⁷ may combine with each other to form a carbon ring or heterocyclic ring having 5 to 12 carbon atoms; R ⁶ and R ⁷ are R
² , may form a carbocycle or a heterocycle together with R ³ .
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 represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group. Represents a group, e represents an integer of 0 to 4, f represents an integer of 0 to 20, and g represents an integer of 0 to 2000. ) Represents a group selected from. Among 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 by R ¹ . Further, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. or,
When Z ¹ and Z ² are a substituted or unsubstituted aliphatic divalent group, a hydroxy group is removed from the diol when X is an aliphatic divalent group or a cycloaliphatic divalent group. A valent group can be mentioned. When Z ¹ and Z ² are a substituted or unsubstituted arylene group, a divalent group derived from a substituted or unsubstituted aryl group defined by R ¹ can be mentioned.

Typical examples of preferable diols when X is an aromatic divalent group are bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane and 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-dityl-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'-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'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone , 3,3'-Dimethyl-4,4 '
-Dihydroxydiphenyl sulfone, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfone,
3,3'-dichloro-4,4'-dihydroxydiphenyl sulfone, 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-dihydroxydibenzo-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, resorcin, 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. An aromatic diol compound containing an ester bond, which is produced by the reaction of 2 mol of diol and 1 mol of isophthaloyl chloride or terephthaloyl chloride is also useful. The constitutional unit of the general formula (II) has been described above with reference to the example of the general formula (XI) as the raw material, but the same symbols have the same definitions in other general formulas.

In the copolymerized polycarbonate resin of the constitutional unit represented by the general formula (I) and the constitutional unit represented by the general formula (II), the proportion of the constitutional unit represented by the general formula (I) is arbitrary. The content of the constituent unit of the general formula (I) corresponds to the charge transporting property of the polycarbonate resin, but is preferably 5 mol% or more, more preferably 20 mol% in all constituent units. It is desirable to contain at least%.

[0031]

The present invention will be described below with reference to examples. In the following examples, all parts are parts by weight. Example 1 N- {4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl} -N, N-bis (4-) having a structure shown in A-1 of Table 2 as a diol having charge transporting ability Tolyl) amine (4.84 parts) was dissolved in dehydrated tetrahydrofuran (THF) (40 parts), and triethylamine (3.06 parts) was added with stirring in a room gas flow, followed by diethylene glycol bischloroformate (2.32 parts). A liquid dissolved in 8 parts of THF was added dropwise at 20 ° C. over 30 minutes. Then, the mixture was reacted with stirring at room temperature for another hour, and 1 part of a THF solution of 4% by weight of phenol was added to terminate the reaction. Then, the precipitated salt was removed by filtration, and the obtained reaction solution was added dropwise to a large amount of methanol to cause precipitation to obtain a yellow polycarbonate resin. After that, the reprecipitation operation of dropping a solution dissolved in THF into methanol to cause precipitation was repeated twice for purification to obtain an alternating copolymer polycarbonate resin (Resin No. 1) shown in Table 3. When the molecular weight of this resin was measured by gel permeation chromatography, the polystyrene equivalent molecular weight was 17,000 in number average molecular weight and 32300 in weight average molecular weight. Further, the glass transition temperature obtained from the differential scanning calorimetry was 119.2 ° C. The infrared absorption spectrum of this resin is shown in FIG. 1, and absorption of C═O stretching vibration attributed to a carbonate group was observed at 1760 cm ⁻¹ . Table 3 shows the results of elemental analysis. It was in agreement with the value calculated as a polycarbonate resin consisting of 1 repeating unit.

Examples 2 to 25 By changing the kind of diol having charge transfer ability shown in Table 2 or by changing the kind of bischloroformate derived from other diol to be copolymerized, or by changing bischloro Resin No. 3 was prepared in the same manner as in Example 1 except that trichloromethylchloroformate, which is a dimer of phosgene, was used in place of formate. 2 to 25 polycarbonate resins were obtained. The infrared absorption spectra of these resins are shown in FIGS. Table 3 also shows the number average molecular weight, weight average molecular weight, elemental analysis value, and glass transition temperature of these resins.

Example 26 N- {4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl} -N, N- having the structure shown in A-1 of Table 2 as a diol having charge transporting ability 3.46 parts of bis (4-tolyl) amine and 1,1 as a copolymerized diol
-Bis (4-hydroxyphenyl) cyclohexane 2.
54 parts and 0.01 part of 4-tert-butylphenol as a molecular weight regulator were put into a stirring reaction vessel, and 2.7 parts of sodium hydroxide and 0.05 part of sodium hydrosulfite were added to 60 parts of water under a nitrogen atmosphere. The dissolved liquid was added and heated and stirred to dissolve. Then, the mixture was cooled to 6 ° C., and a solution prepared by dissolving 2.96 parts of bis (trichloromethyl) carbonate, which is a trimer of phosgene, in 40 parts of dichloromethane was added dropwise over 15 minutes with vigorous stirring to form an emulsion. It was made to react. After completion of the dropping, the mixture was stirred for 15 minutes, 0.7 part of sodium hydroxide was added, and further stirred for 15 minutes, and 0.005 part of triethylamine was added to add 30 parts.
The mixture was reacted with stirring at 90 ° C for 90 minutes. Then, dichloromethane 2
50 parts was added and the organic layer was separated. The organic layer was washed successively with a 5% aqueous sodium hydroxide solution and a 2% aqueous hydrochloric acid solution, and finally with water. This organic layer was dropped into a large amount of methanol to precipitate a yellow polycarbonate resin, and a random copolymer polycarbonate resin (resin No. 26) shown in Table 3 was obtained. The subscript of the repeating unit in the structural formula represents the composition ratio of each structural unit when the number of all repeating units is 1. The results of elemental analysis are shown in Table 3 together with resin No. This value is in agreement with the value calculated for a random copolymerized polycarbonate resin composed of two repeating units each having a composition ratio of 26. When the molecular weight of this resin was measured by gel permeation chromatography, the polystyrene equivalent molecular weight was 106000 in terms of number average molecular weight and 62700 in terms of weight average molecular weight.
It was 0. The glass transition temperature determined from the differential scanning calorimetry was 184 ° C.

Examples 27 to 31 Example 2 was carried out by changing the kind of diol and the composition ratio of constitutional units.
Perform the same operation as in No. 6 to make resin No. 27 to 31 polycarbonate resins were obtained. Infrared absorption spectra of these resins are shown in FIGS. Table 3 also shows the number average molecular weight, weight average molecular weight, elemental analysis value, and glass transition temperature of these resins.

Examples 32 to 35 Example 1 was carried out by changing the type of the diol having the charge transporting ability shown in Table 2 or by changing the type of the bischloroformate derived from the other diol to be copolymerized.
Operate in the same manner as in No. 32-35 polycarbonate resins were obtained. The infrared absorption spectra of these resins are shown in FIGS. Table 3 also shows the number average molecular weight, weight average molecular weight, elemental analysis value, and glass transition temperature of these resins.

Examples 36 to 41 Resin Nos. 36-41 polycarbonate resin was obtained. The infrared absorption spectra of these resins are shown in FIG.
~ 41. Table 3 also shows the number average molecular weight, weight average molecular weight, elemental analysis value, and glass transition temperature of these resins.

[0037]

[Table 2- (1)]

[0038]

[Table 2- (2)]

[0039]

[Table 2- (3)]

[0040]

[Table 2- (4)]

[0041]

[Table 2- (5)]

[0042]

[Table 3- (1)]

[0043]

[Table 3- (2)]

[0044]

[Table 3- (3)]

[0045]

[Table 3- (4)]

[0046]

[Table 3- (5)]

[0047]

[Table 3- (6)]

[0048]

[Table 3- (7)]

[0049]

[Table 3- (8)]

[0050]

[Table 3- (9)]

[0051]

[Table 3- (10)]

[0052]

[Table 3- (11)]

[0053]

[Table 3- (12)]

[0054]

[Table 3- (13)]

[0055]

[Table 3- (14)]

[0056]

[Table 3- (15)]

[0057]

[Table 3- (16)]

[0058]

[Table 3- (17)]

[0059]

[Table 3- (18)]

[0060]

[Table 3- (19)]

Application Example A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a mixed solvent of methanol / butanol was applied on an aluminum plate with a doctor blade, and naturally dried to form an intermediate layer of 0.3 μm. On this, a bisazo compound represented by the following formula as a charge generating substance was crushed by a ball mill in a mixed solvent of cyclohexanone and 2-butanone, and the obtained dispersion was coated with a doctor blade and air-dried to give a 0.2.
A 5 μm charge generation layer was formed.

Embedded image Next, the resin N obtained in Example 1 was used as a charge transport material.
o. The polycarbonate resin of No. 1 is dissolved in dichloromethane, and the solution is applied onto the charge generation layer with a doctor blade, naturally dried, and then dried at 120 ° C. for 20 minutes to form a charge transport layer having a thickness of 20 μm and exposed to light. Body No. 1
Was produced. Photoreceptor No. Regarding No. 1, after using a commercially available electrostatic copying paper testing device [SP428 type manufactured by Kawaguchi Electric Co., Ltd.] for 20 seconds to perform corona discharge of -6 KV in the dark, the surface potential V _{m of the} photoconductor was measured.
(V) was measured, and after being left in the dark for 20 seconds, the surface potential V ₀ (V) was measured. Then, a tungsten lamp light is irradiated so that the illuminance on the surface of the photoconductor becomes 4.5 lux, and the time (second) until V ₀ becomes 1/2 is obtained, and the exposure amount E _1/2 (lux. sec) was calculated. The results are shown below. V _m = −1553V V ₀ = −1239V, E _1/2 = 1.12lux · sec Further, after charging the above photoconductor using a commercially available electrophotographic copying machine, light irradiation is performed through the original drawing. To form an electrostatic latent image, the image was developed using a dry developer, and the obtained image (toner image) was electrostatically transferred onto plain paper and fixed, whereby a clear transferred image was obtained. Similarly, when a wet type developer was used as the developer, a clear transfer image was obtained.

[0062]

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

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram (KBr tablet method) of an aromatic polycarbonate resin (No. 1) obtained in Example 1.

FIG. 2 is an infrared absorption spectrum diagram (KBr tablet method) of the aromatic polycarbonate resin (No. 2) obtained in Example 2.

FIG. 3 is an infrared absorption spectrum diagram (KBr tablet method) of the aromatic polycarbonate resin (No. 3) obtained in Example 3.

FIG. 4 is an infrared absorption spectrum diagram (KBr tablet method) of the aromatic polycarbonate resin (No. 4) obtained in Example 4.

FIG. 5 is an infrared absorption spectrum diagram of the aromatic polycarbonate resin (No. 5) obtained in Example 5 (cast film on a NaCl plate).

FIG. 6 is an infrared absorption spectrum diagram of the aromatic polycarbonate resin (No. 6) obtained in Example 6 (cast film on NaCl plate>

FIG. 7 is an infrared absorption spectrum diagram of the aromatic polycarbonate resin (No. 7) obtained in Example 7 (cast film on a NaCl plate).

FIG. 8 is an infrared absorption spectrum diagram of the aromatic polycarbonate resin (No. 8) obtained in Example 8 (cast film on a NaCl plate).

FIG. 9 is an infrared absorption spectrum diagram of the aromatic polycarbonate resin (No. 9) obtained in Example 9 (cast film on a NaCl plate).

10 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 10) obtained in Example 10. FIG.
Cast film on 1 plate)

FIG. 11 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 11) obtained in Example 11.
Cast film on 1 plate)

FIG. 12 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 12) obtained in Example 12.
Cast film on 1 plate)

FIG. 13 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 13) obtained in Example 13.
Cast film on 1 plate)

FIG. 14 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 14) obtained in Example 14.
Cast film on 1 plate)

FIG. 15 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 15) obtained in Example 15.
Cast film on 1 plate)

16 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 16) obtained in Example 16. FIG.
Cast film on 1 plate)

FIG. 17 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 17) obtained in Example 17.
Cast film on 1 plate)

FIG. 18 is an infrared absorption spectrum diagram (KBr) of the aromatic polycarbonate resin (No. 18) obtained in Example 18.
Tablet method)

FIG. 19 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 19) obtained in Example 19.
Cast film on 1 plate)

FIG. 20 is an infrared absorption spectrum diagram (NaCl) of the aromatic polycarbonate resin (No20) obtained in Example 20.
Cast film on board)

21 is an infrared absorption spectrum diagram (KBr) of the aromatic polycarbonate resin (No. 21) obtained in Example 21. FIG.
Tablet method)

FIG. 22 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 22) obtained in Example 22.
Cast film on 1 plate)

FIG. 23 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 23) obtained in Example 23.
Cast film on 1 plate)

FIG. 24 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 24) obtained in Example 24.
Cast film on 1 plate)

FIG. 25 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 25) obtained in Example 25.
Cast film on 1 plate)

FIG. 26 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 26) obtained in Example 26.
Cast film on 1 plate)

FIG. 27 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 27) obtained in Example 27.
Cast film on 1 plate)

28 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 28) obtained in Example 28. FIG.
Cast film on 1 plate)

FIG. 29 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 29) obtained in Example 29.
Cast film on 1 plate)

FIG. 30 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 30) obtained in Example 30.
Cast film on 1 plate)

FIG. 31 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 31) obtained in Example 31.
Cast film on 1 plate)

FIG. 32 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 32) obtained in Example 32.
Cast film on 1 plate)

FIG. 33 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 33) obtained in Example 33.
Cast film on 1 plate)

34 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 34) obtained in Example 34. FIG.
Cast film on 1 plate)

FIG. 35 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 35) obtained in Example 35.
Cast film on 1 plate)

FIG. 36 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 36) obtained in Example 36.
Cast film on 1 plate)

FIG. 37 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 37) obtained in Example 37.
Cast film on 1 plate)

38 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 38) obtained in Example 38. FIG.
Cast film on 1 plate)

39 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 39) obtained in Example 39. FIG.
Cast film on 1 plate)

FIG. 40 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 40) obtained in Example 40.
Cast film on 1 plate)

FIG. 41 is an infrared absorption spectrum diagram (NaC) of the aromatic polycarbonate resin (No. 41) obtained in Example 41.
Cast film on 1 plate)

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Hiroshi Tamura 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh (72) Inventor Tetsuro Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Shares Inside Ricoh Company (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh (72) Inventor Chihaya Adachi 1-3-6 Nakamagome, Tokyo Ota-ku Stock Company (72) Inventor Chiaki 1-3-6 Nakamagome Nakatamagome, Ota-ku, Tokyo (72) Inventor Akira Katayama 1-3-3 Nakamagome Nakatagome, Ota-ku, Tokyo (72) Invention Nozomu Tamoto 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (72) Inventor Koji Kishida 1-3-3 Nakamagome, Ota-ku, Tokyo Re Inside the Coe (72) Inventor Mitsutoshi Anzai 66-2 Horikawa-cho, Sachi-ku, Kawasaki-shi, Kanagawa Hodogaya Chemical Industry Co., Ltd. Chemical Industry Co., Ltd.

Claims (9)

[Claims] 1. An aromatic polycarbonate resin containing a structural unit represented by the following general formula (I). Embedded image (In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ¹
Represents a substituted or unsubstituted aryl group, and Ar ² , A
r ³ represents a substituted or unsubstituted arylene group. ) 2. The following general formula (I) and the following general formula (II)
When the composition ratio of the structural unit represented by the general formula (I) is k and the composition ratio of the structural unit represented by the general formula (II) is j, the composition ratio is Is 0 <k /
An aromatic polycarbonate resin in which (k + j) ≦ 1. Embedded image (In the formula, R ¹ , Ar ¹ , Ar ² and Ar ³ are the same as defined above.) (In the formula, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or (Here, 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 0.
Is an integer of 4 to 4, 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- or the following formula: Z ¹ and Z ² represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R 1
⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a C 1 to 5 carbon atom. It represents a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and R ⁶ and R ⁷ may combine with each other to form a carbocycle or heterocycle having 5 to 12 carbon atoms. ⁶ , R ⁷ may form a carbocycle or a heterocycle together with R ² and R ³ , R ¹³ and R ¹⁴ represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ Each independently represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, e is an integer of 0 to 4, and f is 0 to 20.
, And g represents an integer of 0 to 2000. ) Represents a group selected from. ) 3. An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (III). Embedded image (In the formula, R ¹ , Ar ¹ , Ar ² , Ar ³ and X are the same as defined above, and n represents the degree of polymerization and represents an integer of 2 to 5000.) 4. An aromatic polycarbonate resin containing a structural unit represented by the following general formula (IV). [Chemical 6] (In the formula, Ar ² and Ar ³ are the same as defined above, and Ar ⁴
Represents a substituted or unsubstituted arylene group. R ¹⁷ , R ¹⁸
Represent the same or different acyl groups, substituted or unsubstituted alkyl groups, and substituted or unsubstituted aryl groups. ) 5. The following general formula (IV) and the following general formula (II):
When the composition ratio of the constitutional unit represented by the general formula (IV) is k and the composition ratio of the constitutional unit represented by the general formula (II) is j, the composition ratio is represented by Is 0 <k /
An aromatic polycarbonate resin in which (k + j) ≦ 1. [Chemical 6] (In the formula, R ¹⁷ , R ¹⁸ , Ar ² , Ar ³ and Ar ⁴ are the same as defined above.) (In the formula, X is the same as the above definition.) 6. An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (V). Embedded image (In the formula, R ¹⁷ , R ¹⁸ , Ar ² , Ar ³ , Ar ⁴ and X are the same as defined above, and n represents the degree of polymerization and represents an integer of 2 to 5000.) 7. An aromatic polycarbonate resin containing a structural unit represented by the following general formula (VI). Embedded image (In the formula, R ¹⁷ and R ¹⁸ are the same as defined above.) 8. The following general formula (VI) and the following general formula (II)
When the composition ratio of the constitutional unit represented by the general formula (VI) is k and the composition ratio of the constitutional unit represented by the general formula (II) is j, the composition ratio is represented by Is 0 <k /
An aromatic polycarbonate resin in which (k + j) ≦ 1. Embedded image (In the formula, R ¹⁷ and R ¹⁸ are the same as defined above.) (In the formula, X is the same as the above definition.) 9. An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (VII). Embedded image (In the formula, R ¹⁷ , R ¹⁸ , and X are the same as defined above, and n is a degree of polymerization and represents an integer of 2 to 5000.)