JPH09302084A - Aromatic polycarbonate resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an arom. polycarbonate resin which comprises repeating units represented by a specific formula and gives a photoreceptor having a high sensitivity by reacting a diol compd. having tert-amino groups with a bischloroformate. SOLUTION: A diol compd. having tert-amino groups and represented by formula I (wherein Ar<1> and Ar<4> are each a divalent arom. hydrocarbon group; and Ar<2> and Ar<3> are aech an arom. hydrocarbon group or a heterocyclic group) and a deoxidizer (e.g. triethylamine) are dissolved in tetrahydrofuran, etc., to give a soln. A soln. of diethylene glycol bischloroformate, etc., in tetrahydrofuran is dropped into the above-prepd. soln., which is then stirred for a certain time. The resultant viscous product is subjected to precipitation in methanol. The obtd. precipitate is filtered to give an arom. polycarbonate resin comprising repeating units represented by formula II [wherein n is 5-500; and X is a divalent aliph. or alicyclic group or a group represented by formula III (wherein R1 and R2 are each alkyl, an arom. hydrocarbon group, or halogen; l and m are each 0-4; and Y is a single bond, 1-12C alkylene, O, S, SO, etc.)].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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 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,
Examples thereof include a laminated-type 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 a low-molecular weight charge transport material reduces the mechanical strength originally possessed by the binder resin, which causes deterioration of wear of the photoreceptor, scratches, cracks, etc., and impairs the durability of the photoreceptor. Has become.

On the other hand, an acrylic resin having polyvinyl anthracene, polyvinyl pyrene, poly-N-vinylcarbazole, triphenylamine as a side chain [M. Stol
kaet al J. Polym. Sci. , 219
69 (1983)] and aromatic polycarbonate resins having a benzidine structure (Japanese Patent Laid-Open No. 64-9964) have been investigated, but they have not been put to practical use.

[0004]

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

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors, a novel aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I) and the following general formulas (II) and (III) are shown. The inventors have found that the above problems can be solved by a novel aromatic polycarbonate resin composed of repeating units described above, and have reached the present invention. That is, the present invention includes the following (1) to (4). (1) An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I).

[0006]

Embedded image

[In the formula, n represents an integer of 5 to 5,000. Ar ¹ and Ar ⁴ represent the same or different aromatic hydrocarbon divalent groups, and Ar ² and Ar ³ 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

[0008]

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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, and 1 and m are each independently 0. an to 4 integer, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -,

[0010]

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Z represents 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 independently substituted or unsubstituted. Represents an alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. (2) It consists of 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.

[0012]

[Chemical 12]

[Wherein k is an integer of 5 to 5000 and j is 5]
Represents an integer of ˜5000. Ar ¹ and Ar ⁴ represent the same or different aromatic hydrocarbon divalent groups, and Ar ² and Ar ³ 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

[0014]

Embedded image

(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, and l and m are each independently 0. an to 4 integer, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -,

[0016]

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, and R ³ and R ⁴ are independently substituted or unsubstituted. Represents an alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. (3) The aromatic polycarbonate resin according to (1) above, which comprises a repeating unit represented by the following general formula (IV).

[0018]

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

[0020]

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[In the formula, k, j, Ar ² , Ar ³ and X have the same meanings as in the above (2)] The aromatic polycarbonate resin of the present invention comprises a known method for producing a polycarbonate resin, which comprises a known bisphenol and a carbonate derivative. It can be produced by the same method as polymerization. That is, it is produced by a transesterification method of a diol compound having a tertiary amino group represented by the following general formula (VI) or general formula (VII) and a bisaryl carbonate, or a phosgene method by solution or interfacial polymerization with phosgene. To be done. In the production by the phosgene method, the following general formula (VIII)
An aromatic polycarbonate resin comprising a repeating unit having a tertiary amino group represented by the general formula (II) and a repeating unit represented by the general formula (III) by using the diol compound represented by An aromatic polycarbonate resin comprising a repeating unit having a tertiary amino group represented by (V) and a repeating unit represented by the above general formula (III) can be produced, and by doing so, a desired property is provided. An aromatic polycarbonate resin is obtained. The above general formula (II)
The ratio of the repeating unit having a tertiary amino group represented by and the repeating unit represented by the general formula (III), and the repeating unit having a tertiary amino group represented by the general formula (V) and the general formula The ratio with the repeating unit represented by (III) can be selected from a wide range depending on the desired characteristics.

[0022]

Embedded image

HO-X-OH (VIII) [Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and X in each formula have the same meanings as defined above. Specific examples of the diol compound having a tertiary amino group represented by the general formula (VI) and the general formula (VII) are shown below. A
Specific examples of the case where r ² and Ar ³ are a substituted or unsubstituted aromatic hydrocarbon group and a substituted or unsubstituted heterocyclic group are as follows.

As the aromatic hydrocarbon group, a phenyl group,
As the condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, a biphenylyl group as a non-condensed polycyclic group, a terphenylyl group, or

[0025]

Embedded image

Here, W is -O-, -S-, -SO-,
-SO ₂ -, - CO- and represent divalent groups below.

[0027]

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And the like. R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group. Further, as the divalent group of the aromatic hydrocarbon represented by Ar ¹ and Ar ⁴ , the above Ar ² and A
The divalent group of the aromatic hydrocarbon group represented by r ³ may be mentioned.
The above-mentioned aromatic hydrocarbon group and heterocyclic group may have a group shown below as a substituent. Further, these substituents are represented as specific examples of R ^{5 in} the above general formula.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) alkyl radical; preferably C ₁ -C ₁₂ especially C ₁ ~
C ₈ and more preferably C _{1 to} C ₄ linear or branched alkyl groups, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C _{1 to} 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, methyl group, 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 group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.

(3) Alkoxy group (-OR ⁷ ); R ⁷ represents the alkyl group defined in (2) above. 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 ~
An alkoxy group having C _4, may contain an alkyl group or a halogen atom C ₁ -C ₄ 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 and a 6-methyl-2-naphthyloxy group. . (5) Substituted mercapto group or aryl mercapto group;
Specific examples include a methylthio group, an ethylthio group, a phenylthio group, a p-methylphenylthio group and the like.

(6)

[0033]

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In the formula, R ⁸ and R ⁹ each independently represent an alkyl group or an aryl group defined in (2), and examples of the aryl group include a phenyl group, a biphenylyl group and a naphthyl group, and these are C ₁ alkoxy group -C _4, alkyl group, or a halogen atom C ₁ -C ₄ may contain a substituent group. R ⁹ and R ¹⁰ may together form a ring. It may also form a ring in cooperation with the carbon atom on the aryl group. Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group, and julolidyl group. Groups and the like.

(7) Examples include an alkylenedioxy group such as a methylenedioxy group, a methylenedithio group, or an alkylenedithio group. Specific examples of the diol compound represented by the general formula (VIII) 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, polytetramethylene ether glycol and other aliphatic diol compounds and 1,4-cyclohexanediol,
1,3-cyclohexanediol, cyclohexane-
Examples thereof include cycloaliphatic diol compounds such as 1,4-dimethanol.

As the diol compound 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′-dihydroxydiphenyl sulfone,
4,4′-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-
Examples thereof include hydroxyphenyl) -tetramethyldisiloxane and phenol-modified silicone oil.

The aromatic polycarbonate resin of the present invention represented by the repeating unit of the general formula (I) is a diol compound having a tertiary amino group represented by the general formula (VI) or (VII), and A bischloroformate derived from a diol compound represented by the formula (VIII),
It can be produced by reacting in the presence of a solvent and a deoxidizing agent.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION The above manufacturing method will be described in more detail below. In the transesterification method, a dihydric phenol and a bisaryl carbonate are mixed in the presence of an inert gas, and usually reacted at 120 to 350 ° C under reduced pressure. 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 a molecular weight regulator and antioxidant as needed. Examples of the bisaryl carbonate include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate,
Examples include di-p-chlorophenyl carbonate and dinaphthyl carbonate.

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 accelerate the reaction, for example, a tertiary amine or a quaternary amine
A catalyst such as a primary ammonium salt can be used, and it is desirable to use a terminal terminating agent such as phenol or p-tert-butylphenol as a molecular weight regulator. 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.

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

The aromatic polycarbonate resin produced by the above method has a number average molecular weight in terms of polystyrene of 1,000 to 1,000,000, preferably 5,000.
~ 500,000. The aromatic polycarbonate resin produced according to the above method, if necessary, an antioxidant,
Additives such as light stabilizers, heat stabilizers, lubricants and plasticizers can be added.

[0043]

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

[0044]

[Chemical 21]

46 ml of dry THF was added to 1,3-bis [N-
5.77 g (0.013 mol) of (3-hydroxyphenyl) -N-phenylamino] benzene and 3.95 g (0.039 mol) of triethylamine were dissolved. 3.33 g (0.0137 mol) of 1,6-hexanediol bischloroformate was added to this solution with dry THF14.
What was melt | dissolved in ml was dripped over 30 minutes under water cooling. After the addition is complete, the viscous mixture is stirred for a further 15 minutes,
0.28 g phenol dissolved in 5 ml dry THF was added. After stirring for 5 minutes, the resulting viscous mixture was precipitated in methanol and the crude product was filtered off. This product was subjected to THF dissolution-methanol precipitation treatment twice,
The precipitate was collected by filtration and dried to obtain a polycarbonate resin (No. 1) having the following structural formula. The obtained target product was 7.19 g and the yield was 90.1%.

[0046]

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. Number average molecular weight 30400 Weight average molecular weight 73900 Glass transition point was 69.8 ° C. The infrared absorption spectrum (film) of this product is shown in FIG. Table 1 shows the results of elemental analysis.

[0048]

[Table 1]

Example 2 The same diol compound having a tertiary amino group as in Example 1 was used as a starting material. 1,3 to 46 ml of dry THF
5.77 g (0.013 mol) of -bis [N- (3-hydroxyphenyl) -N-phenylamino] benzene,
3.95 g (0.039 mol) of triethylamine was dissolved. To this solution was added polytetramethylene ether glycol bischloroformate (prepared from polytetramethylene ether glycol having an average molecular weight of 250) 5.01.
What melt | dissolved g (0.0137 mol) in 14 mL of dry THF was dripped over 30 minutes under water cooling. After the addition was complete, the viscous mixture was stirred for a further 15 minutes and 0.28 g of phenol dissolved in 5 ml of dry THF was added.
After drying for 5 minutes, the resulting viscous mixture was precipitated in methanol and the crude product was filtered off. This product was subjected to a treatment of THF dissolution-methanol precipitation twice, 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 8.22 g, and the yield was 85.8.
%Met.

[0050]

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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 31700 Weight average molecular weight 69200 Glass transition point was 27.7 ° C. The infrared absorption spectrum (film) of this product is shown in FIG. The results of elemental analysis are shown in Table 2.

[0052]

[Table 2]

Example 3 The same diol compound having a tertiary amino group as in Example 1 was used as a starting material. 1,3 to 53 ml of dry THF
-Bis [N- (3-hydroxyphenyl) -N-phenylamino] benzene 6.66 g (0.015 mol),
4.55 g (0.045 mol) of triethylamine was dissolved. 3.65 g (0.0158 mol) of diethylene glycol bischloroformate was dried on this solution.
What was melt | dissolved in HF15ml was dripped over 30 minutes under water cooling. After the addition is complete, the viscous mixture is stirred for a further 15 minutes,
0.28 g phenol dissolved in 5 ml dry THF was added. After drying for 5 minutes, the resulting viscous mixture was precipitated in methanol and the crude product was filtered off. This product was subjected to a treatment of THF dissolution-methanol precipitation twice, and the precipitate was collected by filtration and dried to obtain a polycarbonate resin (No. 3) having the following structural formula. The obtained target product is 7.96.
The yield was 88.2% in g.

[0054]

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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 51700 Weight average molecular weight 98700 Glass transition point was 79.1 ° C. The infrared absorption spectrum (film) of this product is shown in FIG. Table 3 shows the results of elemental analysis.

[0056]

[Table 3]

Examples 4 to 6 The same operation as in Example 1 was carried out to obtain aromatic polycarbonate resins of the present invention shown in the table below. The basic structures of the compounds of Examples 4, 5 and 6 are represented by the following general formula.

[0058]

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The results are shown in Table 4.

[0060]

[Table 4]

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 pulverized in cyclohexanone by a ball mill, and the obtained dispersion was coated with a doctor blade and naturally dried to form a charge generating layer of about 1 μm.

[0062]

[Chemical formula 26]

Next, the polycarbonate resin obtained in Example 5 was dissolved in dichloromethane as a charge transport substance,
This solution was 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 about 20 μm, to prepare a photoreceptor.

In order to examine the sensitivity of the thus obtained laminated type electrophotographic photosensitive member in the visible region, an electrostatic copying paper tester [SP428 type manufactured by Kawaguchi Electric Co., Ltd.] was used for this photosensitive member in the dark. After the corona discharge of −6 kV was performed for 20 seconds for charging, the surface potential V _m (V) of the photoconductor was measured,
After standing in the dark for another 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 V ₀ is 1
The amount of exposure E _1/2 (lux · sec) until it became / 2 was calculated. As a result, V _m = -1415 (V), V _o = -1
It was 036 (V) and E _1/2 = 1.10 (lux · sec).

[0065]

The aromatic polycarbonate resin comprising the repeating unit represented by the general formula (I) of the present invention, 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 composed of and has a charge transporting ability and a high mechanical strength, a photoreceptor using the aromatic polycarbonate resin has high sensitivity and high durability.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the compound of Example 1 of the present invention,

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

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

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

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

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

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Masaomi Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Issei Nagai 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Chihaya Adachi 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Company (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo In Ricoh Co., Ltd. (72) Inventor Akira Katayama 1-3-3 Nakamagome, Ota-ku, Tokyo In Ricoh Co., Ltd.

Claims (4)

[Claims] 1. An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I). Embedded image [In formula, n represents the integer of 5-5000. Ar ¹ and Ar ⁴ are the same or different aromatic hydrocarbon divalent groups, Ar ²
And Ar ³ 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 (Here, 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 1 and m are each independently 0 to 4 Is an integer, Y is a single bond, 1 to 12 carbon atoms
A linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, ## STR3 ## Z represents a divalent group of an aliphatic hydrocarbon, and a
Is an integer of 0 to 20, b is an integer of 1 to 2000, R ³ , R ⁴
Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. ] 2. An aromatic polycarbonate resin comprising repeating units represented by the following general formulas (II) and (III), wherein the composition ratio of repeating units is 0 <k / (k + j) ≦ 1. Embedded image [In the formula, k represents an integer of 5 to 5000, and j represents an integer of 5 to 5000. Ar ¹ and Ar ⁴ represent the same or different aromatic hydrocarbon divalent groups, and Ar ² and Ar ³ represent the same or different substituted or unsubstituted aromatic hydrocarbon groups or substituted or unsubstituted heterocyclic groups. X is an aliphatic divalent group,
Cycloaliphatic divalent group or (Here, 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 1 and m are each independently 0 to 4 Is an integer, Y is a single bond, 1 to 12 carbon atoms
A linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, embedded image Z represents a divalent group of an aliphatic hydrocarbon, and a
Is an integer of 0 to 20, b is an integer of 1 to 2000, R ³ , R ⁴
Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. ] 3. The aromatic polycarbonate resin according to claim 1, comprising a repeating unit represented by the following general formula (IV). [Chemical 7] [In the formula, n, Ar ² , Ar ³ and X have the same meanings as in claim 1.] 4. The aromatic polycarbonate resin according to claim 2, which comprises repeating units represented by the following general formulas (V) and (III), and has a composition ratio of repeating units of 0 <k / (k + j) ≦ 1. Embedded image [In the formula, k, j, Ar ² , Ar ³ and X have the same meanings as in claim 2]