JP3471170B2 - Aromatic polycarbonate resin - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin, and more particularly to a novel aromatic polycarbonate resin useful as a photoconductor 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,
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 circumstances of the prior art, and provides an aromatic polycarbonate resin which is particularly useful as a charge-transporting polymer material for an organic photoreceptor. Is the purpose.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors, the inventors have found that the above problems can be solved by a novel aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I), and the present invention Came to. That is, the present invention is the following (1) and (2) . (1) An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I).

[0006]

[Chemical 9]

[Wherein n represents an integer of 5 to 5000, R ¹ and R ² represent the same or different acyl groups, substituted or unsubstituted aromatic hydrocarbon groups or substituted or unsubstituted heterocyclic groups, and Ar ¹ , Ar ² and Ar ³ represent the same or different aromatic hydrocarbon divalent groups, and p represents an integer of 1 to 5. X is an aliphatic divalent group, a cycloaliphatic divalent group, or

[0008]

[Chemical 10]

(Wherein R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group, an aromatic hydrocarbon group or a halogen atom, and l and m are each independently an integer of 0-4. Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S
-, - SO -, - SO 2 -,

[0010]

[Chemical 11]

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 ⁵ and R ⁶ are each independently substituted or unsubstituted. Represents an alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. ]

[0012]

[0013]

[0014]

[0015]

[0016]

(2) The aromatic polycarbonate resin according to (1), which comprises a repeating unit represented by the following general formula (II).

[0018]

[Chemical formula 15]

[Wherein R ¹ , R ² and X have the same meanings as in claim 1]

[0020]

The aromatic polycarbonate resin of the present invention can be produced by a conventional method for producing a polycarbonate resin in the same manner as the known polymerization of bisphenol and a carbonic acid derivative. That is, the following general formula (III) or general formula (I
V) a transesterification method of a diol compound having a tertiary amino group and a bisaryl carbonate,
Alternatively, it is produced by a phosgene method by solution with phosgene or interfacial polymerization. In addition, the repeating unit of the general formula (I)
The aromatic polycarbonate resin of the present invention represented by
The tertiary amide represented by the above general formula (III) or (IV)
A diol compound having a mino group and the following general formula (V)
Bischlorophores derived from the indicated diol compounds
To react with mate in the presence of solvent and deoxidizer
Can be manufactured more.

[0022]

[Chemical formula 17]

HO-X-OH (V) [R ¹ , R ² , Ar ¹ , Ar ² , Ar ³ , X and P in each formula are the same as defined above. ] General formula (III) and general formula (I
Specific examples of the diol compound having a tertiary amino group represented by V) are shown below. Specific examples of the case where R ¹ and R ² are a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group include the following.

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]

[Chemical 18]

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

[0027]

[Chemical 19]

And the like. R ⁸ 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. In addition, Ar ¹ , Ar ² and Ar
^The divalent group of the aromatic hydrocarbon group represented by ³ is the above R ¹
And a divalent group of the aromatic hydrocarbon group represented by R ² . 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 ^{7 in} the above general formula.

(1) Halogen atom, cyano group, nitro group. (2) Alkyl group : preferably C _{1 to} C _12, especially C
_{1 to} C ₈ , more preferably a C _{1 to} C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C _{1 to} C ₄ alkoxy group, and a phenyl group. Or 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,
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 and the like can be mentioned.

(3) Alkoxy group (-OR ⁹ ) : R ⁹ 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,
Examples thereof include a 2-cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group and a trifluoromethoxy group. (4) Aryloxy group : Examples of the aryl group include a phenyl group and a naphthyl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4
-Methylphenoxy group, 4-methoxyphenoxy group, 4
Examples include -chlorophenoxy group and 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)

[0031]

[Chemical 20]

In the formula, R ¹⁰ and R ¹¹ 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 ¹⁰ and R ¹¹ 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, an alkylenedithio group, and the like.

Specific examples of the diol compound represented by the general formula (V) 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 Examples thereof include aliphatic diol compounds such as polytetramethylene ether glycol and cyclic aliphatic diol compounds such as 1,4-cyclohexanediol, 1,3-cyclohexanediol and cyclohexane-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'-dihydroxydiphenyl sulfoxide, 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 above manufacturing method will be described in more detail below.

In the transesterification method, 2 in the presence of an inert gas.
The dihydric phenol and bisaryl carbonate are mixed 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. Reaction time is usually 1
It is about 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 and di-p.
-Chlorophenyl carbonate, dinaphthyl carbonate, etc. may be mentioned.

In the phosgene method, the reaction is usually performed 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. Additives such as an antioxidant, a light stabilizer, a heat stabilizer, a lubricant, and a plasticizer can be added to the aromatic polycarbonate resin produced according to the above method, if necessary.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to Examples. In the following examples, all parts are parts by weight. Example 1 1,1-bis (4-hydroxyphenyl) under a nitrogen stream
3.80 g (7.4 mmol) of 4- [4- (di-p-tolylamino) phenyl] butane and 2.25 g (22.2 mmol) of triethylamine were dissolved in 30 ml of dry tetrahydrofuran (hereinafter referred to as THF), Diethylene glycol bis (chloroformate) 1.71
A solution of g (7.4 mmol) dissolved in 6 ml of dry THF was added dropwise at 19.0 to 21.0 ° C over 30 minutes. After the dropping, the mixture was stirred at room temperature for 30 minutes, and then a solution of 0.03 g (0.3 mmol) of phenol in 0.7 ml of THF was added and stirred for 10 minutes. Next, the precipitated triethylamine hydrochloride was removed by filtration, the THF solution was added dropwise to methanol, and the precipitated resin was filtered off. Then THF
-Reprecipitation purification with methanol was repeated twice, and heating and drying under reduced pressure gave 4.60 g (yield 92.6%) of the aromatic polycarbonate resin of the present invention represented by the following formula. T
The g was 82.2 ° C.

[0040]

[Chemical 21]

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 1.4 × 10 ⁴ Weight average molecular weight 3.1 × 10 ⁴ The infrared absorption spectrum (KBr tablet method) of this product is shown in FIG. 1, which shows that the C═O stretching vibration of the carbonate at 1760 cm ^−1. Based on absorption. In addition, (C ₄₂ H ₄₁ NO
₇ ) Table 1 shows the elemental analysis results calculated as _n .

[0042]

[Table 1]

Examples 2 to 4 Table 2 was prepared in the same manner as in Example 1 except that the bis (chloroformate) shown in the following table was used instead of the diethylene glycol bis (chloroformate) used in Example 1.
The aromatic polycarbonate resin (No. 2 to 4) shown in was obtained. The structural formulas of these products are shown in Table 2, and the molecular weight of these products in terms of polystyrene measured by gel permeation chromatography, glass transition point, infrared absorption spectrum (KBr tablet method), and elemental analysis results are shown in Table 3. Shown in.

[0044]

[Table 2]

[0045]

[Table 3]

Examples 5 to 10 The diol compounds used in Example 1, 1,1-bis (4-hydroxyphenyl) -4- [4- (di-p-tolylamino) phenyl] butane and diethylene glycol bis (chloroformate) ) Instead of the diol compounds and bis (chloroformates) shown in the table below, the same procedure as in Example 1 was repeated to obtain aromatic polycarbonate resins (Compound Nos. 5 to 10) shown in Tables 4 to 6. Obtained. The structural formulas of these products are also shown in Tables 4 to 6 and the analysis results are shown in Table 7.

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

[Table 6]

[0050]

[Table 7]

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. A bisazo compound represented by the following formula as a charge generating substance was pulverized and dispersed in cyclohexanone as a charge generating substance, and the resulting dispersion was applied with a doctor blade and naturally dried to form a charge generating layer of about 1 μm.

[0052]

[Chemical formula 22]

Next, 1 part of the polycarbonate resin No. 1 obtained in Example 1 as a charge-transporting substance was mixed and dissolved in dichloromethane, and this solution was applied onto the charge-generating layer with a doctor blade, naturally dried, and then dried. 20 at 120 ° C
After drying for a minute, a charge transport layer having a thickness of about 20 μm was formed to prepare a photoreceptor.

For the photoreceptor thus prepared, a commercially available electrostatic copying paper test apparatus [SP42 manufactured by Kawaguchi Electric Co., Ltd.]
Type 8] was used to perform corona discharge of −6 kV in the dark for 20 seconds to charge the surface, and then the surface potential V _m (V) of the photoconductor was measured, and the surface potential was further left for 20 seconds in the dark. V ₀
(V) was measured. Then, the tungsten lamp light is irradiated so that the illuminance on the surface of the photoconductor becomes 4.5 lux,
The time (sec) until V ₀ becomes 1/2 is calculated, and the exposure amount E
_1/2 (lux · sec) was calculated. As a result, V _m =-
1609 (volts), V _o = -1376 (volts), E
_1/2 = 1.24 (lux seconds).

[0055]

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.

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (72) Inventor Chihaya Adachi 1-3-3 Nakamagome, Ota-ku, Tokyo In stock company Ricoh (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh (72) Inventor Hiroshi Tamura 1-3-6 Nakamagome, Ota-ku, Tokyo Inside the formula company Ricoh (72) Inventor Tetsuro Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Inside the Ricoh company (72) Nozomu Tamoto 1-3-6 Nakamagome, Ota-ku, Tokyo Share Company Ricoh (72) Inventor Koji Kishida 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh (72) Inventor Mitsutoshi Anzai 66 2 Horikawa-cho, Sachi-ku, Kawasaki-shi, Kanagawa Hodogaya Chemical Industry Co., Ltd. Incorporated (72) Inventor Akihiro Imai 66-2 Horikawa-cho, Sachi-ku, Kawasaki-shi, Kanagawa Within Hodogaya Chemical Co., Ltd. (56) Reference JP-A-6-295077 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. An aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I). [Chemical 1] [In the formula, n represents an integer of 5 to 5000, R ¹ and R ² represent the same or different acyl groups, substituted or unsubstituted aromatic hydrocarbon groups or substituted or unsubstituted heterocyclic groups,
Ar ¹ , Ar ² and Ar ³ represent the same or different aromatic hydrocarbon divalent groups, and p represents an integer of 1 to 5. X
Is an aliphatic divalent group, a cycloaliphatic divalent group, or (Here, R ³ and R ⁴ 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, and has 1 to 1 carbon atoms
2, 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 ⁵ , R
Each of ⁶ independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. ] 2. The aromatic polycarbonate resin according to claim 1, comprising a repeating unit represented by the following general formula (II) . [Chemical 7] [In the formula, n, R ¹ , R ² and X have the same meanings as in claim 1.]