JP3357557B2 - Aromatic polycarbonate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic polycarbonate resin, and more particularly, to a novel aromatic polycarbonate resin useful as an electrophotographic photoreceptor.

[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 a novel aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I) and a novel aromatic polycarbonate resin represented by the following general formulas (II) and (III) The present inventors have found that the above-mentioned problems can be solved by a novel aromatic polycarbonate resin comprising a repeating unit, and have reached the present invention.

That is, the present invention provides the following (1) to (6). (1) An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I).

[0007]

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[Wherein, n represents an integer of 5 to 5,000. Ar ¹ and Ar ⁵ represent the same or different aromatic hydrocarbon divalent groups or substituted or unsubstituted heterocyclic divalent groups, and Ar ² , Ar ³ , Ar ⁴ and Ar ⁶ represent the same or different substituted or unsubstituted divalent groups. Represents a substituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. X is aliphatic 2
Valent group, cycloaliphatic divalent group, or

[0009]

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(Wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, l and m
Is each independently an integer of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,- SO _2- ,

[0011]

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Z is an aliphatic hydrocarbon divalent group, a is an integer of 0 to 20, b is an integer of 1 to 2000, and R ³ and R ⁴ are each independently substituted or unsubstituted. Represents an alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ). (2) It comprises repeating units represented by the following general formulas (II) and (III), and the composition ratio of the repeating units is 0 <k /
An aromatic polycarbonate resin in which (k + j) ≦ 1.

[0013]

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Wherein k is 5 to 5000 and j is 0 to 50.
Represents an integer of 00. Ar ¹ and Ar ⁵ represent the same or different aromatic hydrocarbon divalent groups or substituted or unsubstituted heterocyclic divalent groups, and Ar ² , Ar ³ , Ar ⁴ and A
r ⁶ represents the same or different substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. X is an aliphatic divalent group, a cycloaliphatic divalent group, or

[0015]

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(Wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, l and m
Is each independently an integer of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,- SO _2- ,

[0017]

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Z is a divalent group of an aliphatic hydrocarbon, a is an integer of 0 to 20, b is an integer of 1 to 2000, and R ³ and R ⁴ are each independently substituted or unsubstituted. Represents an alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ). (3) The aromatic polycarbonate resin according to the above (1), comprising a repeating unit represented by the following general formula (IV).

[0019]

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[Wherein n, Ar ² , Ar ³ , Ar ⁴ , A
r ⁶ and X have the same meanings as in (1) above. (4) Consisting of the repeating units represented by the following formulas (V) and (III), and the composition ratio of the repeating units is 0 <k /
The aromatic polycarbonate resin according to the above (2), wherein (k + j) ≦ 1.

[0021]

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Where k, j, Ar ² , Ar ³ , Ar ⁴ ,
Ar ⁶ and X have the same meanings as in the above (2). (5) The aromatic polycarbonate resin according to the above (1), comprising a repeating unit represented by the following general formula (VI).

[0023]

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(Wherein, n, Ar ² , Ar ⁶ , and X have the same meanings as in the above (1). R ⁵ and R ⁶ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group. A group hydrocarbon group or a halogen atom, and r and s are each independently an integer of 0 to 4.) (6) a repeating unit represented by the following general formulas (VII) and (III), Is 0 <k /
The aromatic polycarbonate resin according to the above (2), wherein (k + j) ≦ 1.

[0025]

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Wherein k, j, Ar ² , Ar ⁶ and X have the same meanings as in the above (2), and R ⁵ , R ⁶ , r and s have the same meanings as in the above (5). Can be produced by a conventional method for producing a polycarbonate resin in the same manner as known polymerization of bisphenol and a carbonic acid derivative. That is, the aromatic polycarbonate resin comprising a repeating unit having a tertiary amino group represented by the general formula (II), (V) or (VII) according to the present invention has the following general formula (VIII),
(IX) A transesterification method of a diol compound having a tertiary amino group represented by (X) or (X) with a bisaryl carbonate, a phosgene method by solution or interfacial polymerization with phosgene, or a bischlorophore derived from a diol It is produced by a bischloroformate method using a mate. At this time, a diol represented by the following general formula (XI) is used in combination to form a repeating unit having a tertiary amino group represented by the above general formula (II) and a repeating unit represented by the above general formula (III) An aromatic polycarbonate resin, a repeating unit having a tertiary amino group represented by the above general formula (V), and a compound represented by the above general formula (II)
An aromatic polycarbonate resin comprising a repeating unit represented by I) or an aromatic polycarbonate comprising a repeating unit having a tertiary amino group represented by the above general formula (VII) and a repeating unit represented by the above general formula (III) A resin can be produced, and in this way, an aromatic polycarbonate resin having desired properties can be obtained. The proportion of the repeating unit having the tertiary amino group represented by the general formula (II) to the repeating unit represented by the general formula (III), and having the tertiary amino group represented by the general formula (V) The ratio of the repeating unit to the repeating unit represented by the general formula (III),
The ratio between the repeating unit having a tertiary amino group represented by the general formula (VII) and the repeating unit represented by the general formula (III) can be selected from a wide range depending on desired characteristics.

In addition, the above general formula (I), (IV) or (V
The aromatic polycarbonate resin comprising a repeating unit having a tertiary amino group represented by I) is a diol compound having a tertiary amino group represented by the following general formula (VIII), (IX) or (X): It can be obtained by interfacial polymerization or solution polymerization with bischloroformate derived from the following general formula (XI). In addition, general formulas (VIII) and (IX)
Alternatively, it can be obtained by polymerization of a bischloroformate derived from a diol compound having a tertiary amino group represented by (X) and a diol represented by the following general formula (XI).

[0028]

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HO—X—OH (XI) [wherein Ar ^{1 to} Ar ⁶ , R ⁵ , R ⁶ , X, r and s are
Same as previous definition . Hereinafter, the above manufacturing method will be described in more detail.

In the transesterification method, a diol compound and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually carried out at 120 to 350 ° C. under reduced pressure. 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. Reaction time is usually 1
About 4 hours. Further, if necessary, a molecular weight regulator and an antioxidant may be added. As the bisaryl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p
-Chlorophenyl carbonate, dinaphthyl carbonate and the like.

In the phosgene method, the reaction is usually carried out in the presence of a deoxidizing agent and a solvent. As the deoxidizing agent, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used. As the solvent, for example, a halogenated hydrocarbon such as dichloromethane or chlorobenzene is used. In order to promote the reaction, for example, tertiary amine, quaternary amine,
A catalyst such as a quaternary ammonium salt can be used, and it is desirable to use a terminal stopper such as phenol or p-tert-butylphenol as a molecular weight regulator. 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.

When bischloroformate is used, it can be obtained by dissolving a diol compound in a solvent, adding a deoxidizing agent, and then adding bischloroformate. Tertiary amines such as trimethylamine, triethylamine and tripropylamine and pyridine are used as the deacidifier. 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 are preferable. or,
Examples of the molecular weight regulator include phenol and p-tert.
It is desirable to use a terminal terminator such as -butylphenol. The reaction temperature is usually 0 to 40 ° C, and the reaction time is several minutes to
5 hours.

If necessary, 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. Hereinafter, the aromatic polycarbonate resin of the present invention will be described in more detail.

The aromatic polycarbonate resin of the present invention comprises
A homopolymer comprising a repeating unit represented by the general formula (II), (V) or (VII), or an alternating copolymer comprising a repeating unit represented by the general formula (I), (IV) or (VI) And a random or block copolymer having a repeating unit represented by formulas (II) and (III), formulas (V) and (III) or formulas (VII) and (III) as a structural unit. Any of polymers may be used. The molecular weight of the aromatic polycarbonate resin of the present invention is 1000 to 1000 in terms of polystyrene equivalent number average molecular weight.
1,000,000, preferably 5,000 to 500,000.

In addition, the aromatic polycarbonate of the present invention comprises the above general formulas (I), (II), (IV), (V),
Specific examples of the tertiary amino group-containing diol compounds represented by the above general formulas (VIII), (IX) and (X), which are the raw materials giving the repeating units represented by (VI) and (VII), are shown below. .

In the general formulas, Ar ² , Ar ³ , Ar ⁴ and Ar ⁶ represent a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. Can be mentioned. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, and a thienyl group and a benzothienyl group as a heterocyclic group. , A furyl group, a benzofuranyl group, a carbazolyl group, and the like. These aromatic groups or heterocyclic groups may have the following groups as substituents.

(1) Halogen atom, cyano group, nitro group. (2) alkyl group; preferably C ₁ -C _12, especially C ₁ -C ₁₂
C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are furthermore a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ alkoxy group, a phenyl group, or It may contain a phenyl group substituted with a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group , 2-methoxyethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl, 4-phenylbenzyl and the like.

(3) alkoxy group (-OR ⁷ ); R ⁷ represents an alkyl group defined in the above (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. This is C ₁ ~
A C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom may be contained as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. .

(5) a substituted mercapto group or an arylmercapto group; specifically, a methylthio group, an ethylthio group,
Examples include a phenylthio group and a p-methylphenylthio group. (6) alkyl-substituted amino group; the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) acyl group; specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

R ¹ and R ² and the substituents R ⁵ and R ⁶ in formula (X) represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. Specific examples thereof are represented by the same definition as the above-mentioned substituted or unsubstituted alkyl group and aromatic group, and specific examples include the same. Further, the aromatic hydrocarbon group may be a phenyl group, which may have a lower alkyl group, a lower alkoxy group and a halogen atom as substituents.

In each formula, Ar represents an aromatic divalent group.
Specific examples of ¹ and Ar ⁵ include benzene, naphthalene, biphenyl, terphenyl, pyrene, fluorene, 9,9
Dimethylfluorene and the like; and heterocyclic groups such as thiophene, benzothiophene, furan, benzofuran and carbazole, and diphenylether and diphenylthioether such as diphenylether and diphenylthioether in which two aryl groups are bonded by oxygen and sulfur.
Represents a valent group. These arylene groups may have an alkyl group, an alkoxy group and a halogen atom as substituents.

As the alkyl group to be a substituent, C _1-
A linear or branched alkyl group of C _5, these alkyl groups may further contain a fluorine atom. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl
-Butyl group, trifluoromethyl group and the like. The alkoxy group to be a substituent is a C _{1 to} C ₅ linear or branched alkoxy group, specifically, a methoxy group,
Ethoxy, n-propoxy, i-propoxy, t
-Butoxy group, n-butoxy group, s-butoxy group, i-
Butoxy group and the like.

Specific examples of the diol compound represented by the general formula (XI) are shown below. 1,3-propanediol, 1,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, 1,8-octanediol,
1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol And aliphatic diols such as polytetramethylene ether glycol and cyclic aliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol and cyclohexane-1,4-dimethanol.

As the diol having an aromatic ring,
4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclopentane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone,
4'-dihydroxydiphenylsulfoxide, 4,4 '
-Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl oxide, 2,2-
Bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, 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.

[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 (A) having a tertiary amino group having the following structure was used as a starting material.

[0047]

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N ', N "-diphenyl-N', N" -bis (4-hydroxyphenyl)-in 40 ml of dry THF
1,4-bis (α-phenylstyryl) benzene-
4.92 g of 4 ′, 4 ″ -diamine (0.00739 mo
l), 2.12 g of triethylamine (0.021 mol
l) was dissolved. 1.70 g of diethylene glycol bischloroformate (0.00735 mol)
l) was dissolved in 8 ml of dry THF, and 8
It was added dropwise over 0 minutes. After completion of the dropwise addition, the viscous mixture was further stirred for 80 minutes, and 0.8 g of a 4 wt% phenol / dry THF solution was added. After stirring for 60 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. 1) having the following structural formula. The obtained target substance is 5.49.
The yield was 81.82% in g and the Tg was 122.5 ° 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 34,000 Weight average molecular weight 161300 The infrared absorption spectrum (KBr tablet method) of this product is shown in FIG. 1, and absorption at 1760 cm ^-1 based on C = O stretching vibration of carbonate was observed. Table 1 shows the results of elemental analysis.

[0051]

[Table 1]

Example 2 The same diol having a tertiary amino group as in Example 1 was used as a starting material. N ', N''-in 50 ml of dry THF
5.92 g (0.00739 m) of diphenyl-N ′, N ″ -bis (4-hydroxyphenyl) -1,4-bis (α-phenylstyryl) benzene-4 ′, 4 ″ -diamine
ol), 2.12 g of triethylamine (0.021 mol
l) was dissolved. To this solution was added polytetramethylene ether glycol bischloroformate (average molecular weight 25
0 from polytetramethylene ether glycol)
2.69 g (0.00735 mol) of dry THF 8m
The mixture was added dropwise over 80 minutes while cooling with water.
After completion of the dropwise addition, the viscous mixture was further stirred for 80 minutes,
0.8 g of phenol / dry THF was added. After stirring for 60 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 product was 4.84 g, the yield was 63.21%, and the glass transition point was 86.9 ° C.

[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 30417 Weight average molecular weight 99227 The infrared absorption spectrum (KBr tablet method) of this product is shown in FIG. 2, and absorption at 1760 cm ^-1 based on C = 0 stretching vibration of carbonate was observed. Table 2 shows the results of elemental analysis.

[0055]

[Table 2]

Examples 3 and 4 The procedure of Example 1 was repeated, except that the bischloroformate was used, to obtain aromatic polycarbonate resins of the present invention shown in the following table. The basic structures of the compounds of Examples 3 and 4 are represented by the following general formula.

[0057]

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Table 3 shows the results.

[0059]

[Table 3]

Example 5 A polymerization reaction was carried out in the same manner as in Example 3. However, a diol compound (B) having a tertiary amino group having the following structure was used as a starting material.

[0061]

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The obtained target product (No. 5) was 4.63 g and the yield was 97.9%. The glass transition temperature is 149.
1 ° C. The target product (No. 5) is represented by the following structural formula.

[0063]

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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. Weight average molecular weight 13.9 × 10 ⁴ Number average molecular weight 1.82 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 0 cm ⁻¹ , absorption based on C ＝ O stretching vibration of carbonate was observed. Table 4 shows the results of elemental analysis.

[0065]

[Table 4]

Examples 6 to 8 Polymerization was carried out in the same manner as in Examples 1 to 3. However, a diol compound having a tertiary amino group having the following structure (C)
Was used as starting material.

[0067]

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The basic structures of the objects of Examples 6 to 8 are represented by the following general formulas (No. 6 to No. 8).

[0069]

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[0070]

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Table 5 shows the results.

[0072]

[Table 5]

Example 9 N ', N "-diphenyl-N', N" -bis (4-hydroxyphenyl) -1,4-bis (α-phenylstyryl) benzene-4 ', 4 "-diamine 60 g (0.
002 mol) in a reaction vessel, and 0.32 g (0.008 mol) of sodium hydroxide in 30 m of ion-exchanged water.
An aqueous solution dissolved in 1 was added and stirred. Under ice cooling, a solution of 0.356 g (0.0012 mol) of triphosgene dissolved in 10 ml of methylene chloride was slowly added dropwise over 20 minutes. While rinsing the vessel, 5 ml of methylene chloride was added. And 0.1 g of sodium hydroxide at room temperature
(0.025 mol). Further, one drop of triethylamine was added, and the mixture was stirred for 2 hours. The resulting viscous mixture was washed with a 5% aqueous sodium hydroxide solution, a 2% aqueous hydrochloric acid solution, and ion-exchanged water. A precipitate reprecipitated in methanol was collected by filtration, dried, and dried with a polycarbonate resin having the following structural formula ( No. 9) was obtained. The obtained target product was 1.25 g and the yield was 75.3%. Glass transition temperature is 201.5 ° C
Met.

[0074]

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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. Weight average molecular weight 18.3 × 10 ⁴ Number average molecular weight 2.33 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 0 cm ⁻¹ , absorption based on C ＝ O stretching vibration of carbonate was observed. Table 6 shows the results of elemental analysis.

[0076]

[Table 6]

Example 10 A polymerization reaction was carried out in the same manner as in Example 9. However, the diol compound (B) having a tertiary amino group of the structure (B) was used as a starting material. The obtained target substance (No.
10) was 0.91 g, and the yield was 53.2%. The glass transition temperature was 198.0 ° C.

[0078]

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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. Weight average molecular weight 2.69 × 10 ⁴ Number average molecular weight 0.50 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 60 cm ^-1 , absorption based on C = O stretching vibration of carbonate was observed. Table 7 shows the results of elemental analysis.

[0080]

[Table 7]

Example 11 N ', N "-bis (4-methylphenyl) -N', N"
-Bis (4-hydroxyphenyl) -1,4-bis (α
-Phenylstyryl) benzene-4 ', 4 "-diamine 5.14 g (0.006 mol) and bisphenol C
1.54 g (0.006 mol) was placed in a reaction vessel, and an aqueous solution in which 1.92 g (0.048 mol) of sodium hydroxide was dissolved in 800 ml of ion-exchanged water was added and stirred.
Triphosgene 2.14 g (0.0012 mol) under ice-cooling
In 500 ml of methylene chloride was slowly added dropwise over 60 minutes. 100ml while rinsing the container
Methylene chloride was added. Then, 0.6 g of sodium hydroxide was added at room temperature. Further, one drop of triethylamine was added, and the mixture was stirred for 5 hours. The resulting viscous mixture was washed with a 5% aqueous sodium hydroxide solution, a 2% aqueous hydrochloric acid solution, and ion-exchanged water. A precipitate reprecipitated in methanol was collected by filtration, dried, and dried with a polycarbonate resin having the following structural formula ( N
o.11). The obtained target product was 5.11 g and the yield was 73.1%. The glass transition temperature was 182.6 ° C.

[0082]

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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. Weight average molecular weight 22.5 × 10 ⁴ Number average molecular weight 1.53 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 60 cm ^-1 , absorption based on C = O stretching vibration of carbonate was observed. Table 8 shows the results of elemental analysis.

[0084]

[Table 8]

Example 12 A tertiary amino group-containing diol compound (D) having the following structure was used as a starting material.

[0086]

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The above diol 5.6 was added to 40 ml of dry THF.
4 g (0.005 mol), triethylamine 1.52
g (0.015 mol) was dissolved. 1.21 g of diethylene glycol bischloroformate was added to this solution.
(0.005 mol) dissolved in 10 ml of dry THF was added dropwise over 30 minutes while cooling with water. After dropping,
The viscous mixture was further stirred for 120 minutes and 0.8 g of a 4 wt% phenol / dry THF solution was added. After stirring for 120 minutes, the resulting viscous mixture was washed with a 5% aqueous sodium hydroxide solution, a 2% aqueous hydrochloric acid solution, and ion-exchanged water, reprecipitated in methanol, and collected by filtration. After drying, a polycarbonate resin (No. 12) having the following structural formula was obtained. The obtained target product was 5.83 g and the yield was 88.6%. Glass transition temperature was 150.0 ° C.

[0088]

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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. Weight average molecular weight 12.8 × 10 ⁴ Number average molecular weight 1.87 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 60 cm ^-1 , absorption based on C = O stretching vibration of carbonate was observed. Table 9 shows the results of elemental analysis.

[0090]

[Table 9]

Examples 13 to 14 An aromatic polycarbonate resin of the present invention shown in the following table was obtained in the same manner as in Example 12 except that the bischloroformate was changed. Examples 13 and 1
The basic structure of the compound of No. 4 is represented by the following general formula (Nos.
14).

[0092]

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Table 10 shows the results.

[0094]

[Table 10]

The infrared absorption spectra of these compounds are shown in FIGS. 13 and 14. Absorption at 1760 cm ^-1 based on the C = O stretching vibration of carbonate was observed.

Example 15 2.25 g (0.002 mol) of the diol compound (D)
l) into a reaction vessel and add sodium hydroxide 0.32g
(0.008 mol) in 30 ml of deionized water
The aqueous solution was added and stirred. Triphosgene 0.35 under ice cooling
6 g (0.0012 mol) in 10 ml of methylene chloride
The dissolved solution was slowly dropped over 20 minutes. Container
While rinsing, 5 ml of methylene chloride was added. Soshi
And 0.1 g of sodium hydroxide (0.025
mol). Then add a drop of triethylamine,
Stirring was performed for 2 hours. The resulting viscous mixture is treated with 5%
Sodium chloride solution, 2% hydrochloric acid solution, ion exchange water
After washing, the precipitate reprecipitated in methanol is collected by filtration and dried.
After drying, polycarbonate resin of the following structural formula (No. 15)
I got The obtained target product was 1.25 g and the yield was 52.7.
%Met. Glass transition temperature was 192.8 ° C.

[0097]

Embedded image

When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Weight average molecular weight 15.8 × 10 ⁴ Number average molecular weight 1.81 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 75 cm ^-1 , absorption based on C = O stretching vibration of carbonate was observed. Table 11 shows the results of elemental analysis.

[0099]

[Table 11]

Example 16 5.07 g of the diol compound (D) (0.0045 m
ol) and 1.02 g of bisphenol A (0.0045 m
ol) in a reaction vessel, and 0.72 g of sodium hydroxide.
(0.018 mol) in 60 ml of ion-exchanged water was added and stirred. 20 ml of methylene chloride
Was added. Then, 0.80 g of triphosgene under ice cooling
(0.003 mol) in 15 ml of methylene chloride was slowly added dropwise over 60 minutes. While rinsing the vessel, 5 ml of methylene chloride was added. Then, 0.225 g of sodium hydroxide was added at room temperature. Further, one drop of triethylamine was added, and the mixture was stirred for 5 hours. t
-Butylphenol (60 mg) was added, and the mixture was further stirred for 1 hour. The resulting viscous mixture was washed with a 5% aqueous sodium hydroxide solution, a 2% aqueous hydrochloric acid solution, and ion-exchanged water, and the precipitate reprecipitated in methanol was collected by filtration, dried, and dried with a polycarbonate resin having the following structural formula ( No. 16) was obtained. The obtained target product was 5.73 g and the yield was 88.6%. Glass transition temperature was 185.3 ° C.

[0101]

Embedded image

When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Weight average molecular weight 7.90 × 10 ⁴ Number average molecular weight 1.89 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 75 cm ^-1 , absorption based on C = O stretching vibration of carbonate was observed. Table 12 shows the results of elemental analysis.

[0103]

[Table 12]

Example 17 A polymerization reaction was carried out in the same manner as in Example 16 except that bisphenol Z was used instead of bisphenol A. The basic structure of the compound of Example 17 is represented by the following general formula (No. 17). Glass transition temperature is 190.0
° C.

[0105]

Embedded image

When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Weight average molecular weight 6.56 × 10 ⁴ Number average molecular weight 1.16 × 10 ⁴ The infrared absorption spectrum of this product is shown in FIG.
At 75 cm ^-1 , absorption based on C = O stretching vibration of carbonate was observed. Table 13 shows the results of elemental analysis.

[0107]

[Table 13]

Application Example A polyamide resin (CM-8000: manufactured by Toray Industries, Ltd.) solution dissolved in a mixed solvent of methanol and butanol is applied on a 0.2 mm thick aluminum plate by a doctor blade, air-dried, and a 0.3 μm intermediate Layers were provided. 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.

[0109]

Embedded image

Next, 9 parts of methylene dichloride was mixed and dissolved in 1 part of the polycarbonate resin No. 1 obtained in Example 1 as a charge transporting substance, and the solution was applied on the charge generating layer with a doctor blade. For 20 minutes to form a charge transport layer having a thickness of about 20 μm, thereby producing a photoreceptor.

The photoreceptor thus produced was tested with a commercially available electrostatic copying paper tester [SP42 manufactured by Kawaguchi Electric Works, Ltd.]
8 type] and charged in a dark place by performing a −6 kV corona discharge for 20 seconds, and then measuring the surface potential V _m (V) of the photoreceptor. V ₀
(V) was measured. Next, a tungsten lamp light is irradiated so that the illuminance on the photoreceptor surface becomes 4.5 lux,
The time (second) until V ₀ becomes １ ／ is obtained, and the exposure amount E is calculated.
_1/2 (lux · sec) was calculated. As a result, V _o = −
1291 (volt), E _1/2 = 0.74 (look
Seconds).

[0112]

According to the present invention, the aromatic polycarbonate resin comprising the repeating unit represented by the general formula (I) or the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III) Since the aromatic polycarbonate resin of the formula (1) has charge transporting ability and high mechanical strength, the photoreceptor using the resin has high sensitivity and high durability.

[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.

FIG. 11 is an infrared absorption spectrum of the compound of Example 11 of the present invention.

FIG. 12 is an infrared absorption spectrum of the compound of Example 12 of the present invention.

FIG. 13 is an infrared absorption spectrum of the compound of Example 13 of the present invention.

FIG. 14 is an infrared absorption spectrum of the compound of Example 14 of the present invention.

FIG. 15 is an infrared absorption spectrum of the compound of Example 15 of the present invention.

FIG. 16 is an infrared absorption spectrum of the compound of Example 16 of the present invention.

FIG. 17 is an infrared absorption spectrum of the compound of Example 17 of the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsuhiro Morooka, 66-2 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Pref. No. 6 Inside Ricoh Co., Ltd. (72) Tomoyuki Shimada, Inventor 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Chiaki Tanaka 1-3-6, Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd. (72) Nozomi Tamoto 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh Company (72) Akira Katayama 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company (56) References JP-A-8-62864 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY ( STN) WP / L (QUESTEL)

Claims (6)

(57) [Claims] 1. An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I). Embedded image [In the formula, n represents an integer of 5 to 5000. Ar ¹ and Ar ⁵ represent the same or different aromatic hydrocarbon divalent groups or substituted or unsubstituted heterocyclic divalent groups,
² , Ar ³ , Ar ⁴ and Ar ⁶ represent the same or different substituted or unsubstituted aromatic hydrocarbon groups or substituted or unsubstituted heterocyclic groups. X is an aliphatic divalent group, a cycloaliphatic divalent group, or (Where R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, and l and m are each independently 0 to 4 Y is a single bond, having 1 to 1 carbon atoms.
2 linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, ## STR3 ## Wherein Z represents a divalent group of an aliphatic hydrocarbon;
Is an integer of 0 to 20, b is an integer of 1 to 2000, R ³ and R ⁴
Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. )
Represents ] 2. A composition comprising repeating units represented by the following general formulas (II) and (III), wherein the composition ratio of the repeating units is 0:
An aromatic polycarbonate resin in which <k / (k + j) ≦ 1. Embedded image [In the formula, k represents an integer of ⁵ to 5000 and j represents an integer of 0 to 5000. Ar ¹ and Ar ⁵ are the same or different aromatic hydrocarbon divalent groups or substituted or unsubstituted heterocyclic divalent groups. Ar ² , Ar ³ , Ar ⁴ and Ar ⁶ represent the same or different substituted or unsubstituted aromatic hydrocarbon groups or substituted or unsubstituted heterocyclic groups, and X represents an aliphatic divalent group. A cycloaliphatic divalent group, or (Where R ¹ and R ² is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom; l and m are each independently an integer of 0 to 4; Bond, number of carbon atoms 1
~ 12 linear, branched or cyclic alkylene groups,-
O -, - S -, - SO -, - SO 2 -, embedded image Z represents an aliphatic hydrocarbon divalent group, a is an integer of 0 to 20, b is an integer of 1 to 2000, R ³ , R ^3
4 independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. )] 3. The aromatic polycarbonate resin according to claim 1, comprising a repeating unit represented by the following general formula (IV). Embedded image [In the formula, n, Ar ² , Ar ³ , Ar ⁴ , Ar ⁶ , and X have the same meanings as in claim 1] 4. The aromatic polycarbonate resin according to claim 2, comprising a repeating unit represented by the following general formulas (V) and (III), wherein the composition ratio of the repeating unit is 0 <k / (k + j) ≦ 1. Embedded image [Where k, j, Ar ² , Ar ³ , Ar ⁴ , Ar ⁶ and X are the same as in claim 2] 5. The aromatic polycarbonate resin according to claim 1, comprising a repeating unit represented by the following general formula (VI). Embedded image (Wherein, n, Ar ² , Ar ⁶ and X are as defined in claim 1. R ⁵
And R ⁶ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, and r and s are each independently 0 to 4
Is an integer. ) 6. A repeating unit represented by the following general formulas (VII) and (III), wherein the composition ratio of the repeating unit is 0.
3. The aromatic polycarbonate resin according to claim 2, wherein <k / (k + j) ≦ 1. Embedded image (Where k, j, Ar ² , Ar ⁶ , and X are as defined in claim 2,
R ⁵ , R ⁶ , r, s are as defined in claim 5)