JP3358140B2 - Aromatic polycarbonate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic polycarbonate resin, and more particularly, to a novel aromatic polycarbonate resin useful as an organic photoconductive material for an electrophotographic photosensitive member.

[0002]

2. Description of the Related Art As an aromatic polycarbonate resin,
Polycarbonate resins obtained by reacting 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) with a carbonate precursor such as phosgene or diphenyl carbonate are known as typical ones. I have. Since such a polycarbonate resin from bisphenol A has excellent properties such as transparency, heat resistance, dimensional accuracy, and mechanical strength,
It is used in many fields. As one example,
Various studies have been made on binder resins for organic photoreceptors used in electrophotography. As a typical configuration example of the organic photoconductor, there is a stacked photoconductor in which a charge generation layer and a charge transport layer are sequentially stacked 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, due to the inclusion of the low-molecular charge transport material, the mechanical strength inherent in the binder resin is reduced, which results in abrasion of the photoconductor,
This causes scratches, cracks, etc., and impairs the durability of the photoconductor.

On the other hand, acrylic resins having polyvinyl anthracene, polyvinyl pyrene, poly-N-vinyl carbazole, and tertiary amine in the side chain [M. Stolka e
tal, J. et al. Polym. Sci. , Vol 21, 9
69 (1983)] and a photoconductive polymer material such as a polycarbonate resin having a benzidine structure (Japanese Patent Application Laid-Open No. 64-9964) has been studied, but has 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 polymer charge transporting material for an organic photoreceptor. For that purpose.

[0005]

According to the present invention, there are provided structural units represented by the following formulas (Formula 5) and (Formula 6),
An aromatic polycarbonate resin having a phenol-terminated end is provided.

[0006]

Embedded image [In the above formula, Ar ¹ and Ar ² each represent a substituted or unsubstituted aryl group, which may be the same or different. A is a single bond, a substituted or unsubstituted alkylene group, alkylidene group, cycloalkylidene group, an oxygen atom, a sulfur atom, a vinylene group, X is an alkylene group, a polyalkylene ether group or the formula -Ar ³ -Y-Ar ⁴ - (in the formula, Ar
³ , Ar ⁴ represents a substituted or unsubstituted arylene group,
Y may be the same or different, and Y represents a single bond, a substituted or unsubstituted alkylene group, a polyalkylene ether group, an alkylidene group, a cycloalkylidene group, an oxygen atom, a sulfur atom, or a vinylene group. )
R ¹ , R ² and R ³ are a substituted or unsubstituted alkyl group,
Represents an aryl group or a halogen atom, and l, m and n each independently represent an integer of 0 to 3. p is 5 to 5,000
Represents an integer of 0. ]

[0007]

Embedded image [In the above formula, R ⁴ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, and X represents an alkylene group, a polyalkylene ether group, or the following formula: —Ar ³ —Y—Ar ⁴ —
(Wherein, Ar ³ and Ar ⁴ each represent a substituted or unsubstituted arylene group, which may be the same or different, and Y is a single bond, a substituted or unsubstituted alkylene group, a polyalkylene ether group, an alkylidene group, A cycloalkylidene group, an oxygen atom, a sulfur atom, or a vinylene group). ]

Further, according to the present invention, an aromatic polycarbonate resin comprising structural units represented by the following formulas (Formula 7) and (Formula 8), wherein the composition ratio of the structural units is 0 <k / (k + j) ≦ 1 Is provided.

[0009]

Embedded image

[0010]

Embedded image [In the above formula, Ar ¹ and Ar ² each represent a substituted or unsubstituted aryl group, which may be the same or different. A is a single bond, a substituted or unsubstituted alkylene group, alkylidene group, cycloalkylidene group, an oxygen atom, a sulfur atom, a vinylene group, X is an alkylene group, a polyalkylene ether group or the formula -Ar ³ -Y-Ar ⁴ - (in the formula, Ar
³ , Ar ⁴ represents a substituted or unsubstituted arylene group,
Y may be the same or different, and Y represents a single bond, a substituted or unsubstituted alkylene group, a polyalkylene ether group, an alkylidene group, a cycloalkylidene group, an oxygen atom, a sulfur atom, or a vinylene group. )
R ¹ , R ² and R ³ are a substituted or unsubstituted alkyl group,
Represents an aryl group or a halogen atom, and l, m and n each independently represent an integer of 0 to 3. These resins of the present invention have a number average molecular weight of 2000 to 400,000 and a weight average molecular weight of 2500 to 400,000.

Specific examples of R1 to R4, Ar1 and Ar2 in the above formulas (Chemical Formula 5), (Chemical Formula 6), (Chemical Formula 7) and (Chemical Formula 8) include, as an alkyl group, a methyl group, an ethyl group,
Examples of the propyl group, butyl group, and the like, and the aryl group include a phenyl group, a tolyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a pyrenyl group. , An alkoxy group as a methoxy group, an ethoxy group, a propoxy group,
The butoxy group and the like include fluorine, chlorine, bromine and iodine as halogen atoms. Ar3, Ar4
Specific examples thereof include a phenylene group, a biphenylylene group, a naphthylene group and the like, which may further have the substituents described above. Next, as specific examples of A, X and Y, an alkylene group or a polyalkylene ether group such as a dialkylene ether group, a side chain lower alkyl-substituted dialkylene ether group, a trialkylene ether group, a side chain lower alkyl-substituted trialkylene ether group,
Tetraalkylene ether group, methylene group, ethylene group, trimethylene group, tetramethylene group, 2-methyl-trimethylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group as an alkylene group of a side chain lower alkyl-substituted tetraalkylene ether group, Examples thereof include a methoxyethylene group, a phenylmethylene group, a 4-methylphenylmethylene group, and a diphenylmethylene group. Examples of the alkylidene group include an isopropylidene group, an isobutylidene group, and a sec-butylidene group. Examples thereof include a cyclopentylidene group, a cyclohexylidene group, a cyclooctylidene group and the like. The aromatic polycarbonate resin represented by the above formula (Chemical Formula 5) according to the present invention is a novel substance, and is composed of a dihydroxy compound represented by the following Formula (Chemical Formula 9) and a bis (Chemical Formula 10) represented by the following Formula (Chemical Formula 10). (Chloroformate) compound and a deoxidizing agent, and then reacting in the presence or absence of a solvent.

[0012]

Embedded image (In the above formula, Ar ¹ and Ar ² each represent a substituted or unsubstituted aryl group, which may be the same or different. A represents a single bond, a substituted or unsubstituted alkylene group, an alkylidene group, a cycloalkylidene group, an oxygen R ¹ , R ² and R ³ represent a substituted or unsubstituted alkyl group, aryl group or halogen atom, and l, m and n each independently represent an integer of 0 to 3 Represents.)

[0013]

Embedded image [X represents an alkylene group, a polyalkylene ether group or the formula -Ar ³ -Y-Ar ⁴ - (wherein, Ar ^3, Ar ⁴ represents a substituted or unsubstituted arylene group, may each be the same or different , Y represents a single bond, a substituted or unsubstituted alkylene group, a polyalkylene ether group, an alkylidene group, a cycloalkylidene group, an oxygen atom, a sulfur atom, and a vinylene group. Further, the aromatic polycarbonate resin represented by the above formula (Chemical Formula 6) according to the present invention can be obtained by the same production method as in (Chemical Formula 5). The aromatic polycarbonate resin comprising the structural units represented by the formulas (Chem. 7) and (Chem. 8) according to the present invention comprises a dihydroxy compound represented by the formula (Chem. 9) and a dihydroxy compound represented by the following formula (Chem. 11). The compound can be obtained by dissolving the compound in a solvent, adding a deoxidizing agent and introducing phosgene or liquefied phosgene by a conventionally known method.

[0014]

Embedded image (Where X is the same as above)

In these cases, examples of the deoxidizing agent include nitrogen compounds such as triethylamine, triethylamine, tripropylamine, pyridine and quinoline, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The addition amount is usually an amount sufficient to neutralize hydrogen chloride generated during the reaction, specifically, an equivalent to 3 times the amount of the reactive group. Reaction solvents include dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, ethyl ether, toluene, xylene, acetone, methyl ethyl ketone, cyclohexane,
Hexane and the like can be mentioned. Reaction temperature is 0-1
It is performed in the range of 50 ° C.

Further, the aromatic polycarbonate resin represented by the above formulas (Chemical Formula 7) and (Chemical Formula 8) is obtained by using a dihydroxy compound represented by the above formula (Formula 9) and a dihydroxy compound represented by the above formula (Formula 11) in a solvent. It can also be synthesized by dissolving and adding a deoxidizing agent.

The molecular weight of the resin of the present invention is determined by the reaction molar ratio of the dihydroxy compound to the bis (chloroformate) compound or phosgene, or the type and amount of the deoxidizing agent and the reaction solvent, and the combination thereof. The value can be adjusted.

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.

The novel aromatic polycarbonate resin obtained by the present invention is extremely useful as a photoconductive material in an electrophotographic photosensitive member, and is optically or chemically sensitized by a sensitizer such as a dye or a Lewis acid. Is done. Furthermore, this one uses an organic pigment or an inorganic pigment as a charge generating material,
It is particularly useful as a charge transport material in a so-called function-separated type photoconductor.

Examples of the sensitizer include triarylmethane dyes such as methyl violet and crystal violet; xanthene dyes such as rose bengal, erythrosine and rhodamine; 2,4,7-trinitro-9-fluorenone; -Dinitro-9-fluorenone and the like.

As organic pigments, azo pigments such as C.I. Pigment Blue 25 (CI No. 21180), C.I. Pigment Red 41 (CI. No. 21200), C.I. Pigment Red 3 (CI. No. 45210), and C.I. 16 (CI
No. Phthalocyanine-based pigments such as C.I. 74100), indigo-based pigments such as C-I-but Brown 5 (CI No. 73410), C.I. . In addition, inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide, and α-silicon can also be used.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Example 1 Under a nitrogen stream, 8.67 g (10.0 mmol) of 1,1-bis {3- [4-di-tolylaminophenethyl] -4-hydroxyphenyl} cyclohexane and 3.04 g of triethylamine ( 30.0 mmol) was dissolved in 50 ml of dry tetrahydrofuran, and 2.31 g (10.10 g) of diethylene glycol bis (chloroformate) was added thereto.
0 mmol) dissolved in 10 ml of dry tetrahydrofuran was added dropwise at room temperature over 30 minutes. continue,
After stirring at room temperature for 3 hours, phenol 0.04 g
(0.4 mmol) dissolved in 1 ml of tetrahydrofuran was added, and the mixture was further stirred for 10 minutes. next,
The precipitated triethylamine hydrochloride was removed by filtration, the tetrahydrofuran solution of the filtrate was dropped into methanol, and the precipitated resin was separated by filtration and dried by heating under reduced pressure. Further, the operation of dissolving the obtained resin in tetrahydrofuran and precipitating it in methanol is repeated twice, and dried by heating under reduced pressure to 7.92 g of the target aromatic polycarbonate resin represented by the following structural formula (yield: 77.3).
%). Its Tg is 91 ° C., and its number average molecular weight and weight average molecular weight (in terms of polystyrene) are 5
800 and 11900.

[0024]

Embedded image The elemental analysis values of the aromatic polycarbonate resin were as follows. Its infrared absorption spectrum (KBr tablet method) is shown in FIG.
Shown in

Examples 2 to 4 Under the same conditions as in Example 1, other aromatic polycarbonate resins were obtained. The chemical structural formula of the obtained resin is shown in Table 1, and the yield, Tg, number average molecular weight (Mn), and weight average molecular weight (M
Table 2 shows w) and the elemental analysis values.

[0026]

[Table 1]

[0027]

[Table 2] Application Example A polyamide resin (CM-8000: manufactured by Toray Industries, Ltd.) solution dissolved in a mixed solvent of methanol and butanol was applied on an aluminum plate with a doctor blade and air-dried to form a 0.3 μm intermediate layer. A bisazo compound represented by the following formula (Chemical Formula 13) is pulverized in cyclohexanone as a charge generating substance by a ball mill, and the obtained dispersion is applied with a doctor blade and air-dried to form a charge generating layer of about 1 μm. Formed.

[0028]

Embedded image Next, the compound of Example 1 was dissolved in dichloromethane as a charge transport material, and the solution was applied on the charge generation layer with a doctor blade, air-dried, and then dried at 120 ° C. for 2 hours.
After drying for 0 minutes, a charge transport layer having a thickness of about 20 μm was formed to prepare a photoreceptor. Next, in order to examine the sensitivity in the visible region of the laminated electrophotographic photosensitive member thus obtained, an electrostatic copying paper test apparatus, SP428, manufactured by Kawaguchi Electric Works, Ltd.
After charging by performing a −6 KV corona discharge for 20 seconds in a dark place using a mold｝, the surface potential Vm (V) of the photoreceptor is measured.
(V) was measured. Then, a tungsten lamp light is irradiated so that the illuminance on the photoreceptor surface becomes 4.5 lx,
Exposure E1 / 2 (lx · s) until Vo becomes 1/2
Was measured. The results were Vm-1321 (V), Vo-12
33 (V) and E1 / 21.20 (lx · s).

[0029]

As is apparent from the above detailed and specific description, the aromatic polycarbonate resin of the present invention has a charge transporting ability and a high mechanical strength. It is useful as a polymer material.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum diagram (KBr tablet method) of an aromatic polycarbonate resin obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Mitsutoshi Anzai 66-2 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture (72) Inventor Akihiro Imai 66-2 Horikawa-cho, Saiwai-ku, Kawasaki City, Kanagawa Prefecture (56) References JP-A-4-320420 (JP, A) (58) ) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An aromatic polycarbonate resin comprising a structural unit represented by the following formula (Formula 1) and having a number average molecular weight of 2,000 to 400,000 and a weight average molecular weight of 2,500 to 400,000. Embedded image [In the above formula, Ar ¹ and Ar ² each represent a substituted or unsubstituted aryl group, which may be the same or different. A is a single bond, a substituted or unsubstituted alkylene group, alkylidene group, cycloalkylidene group, an oxygen atom, a sulfur atom, a vinylene group, X is an alkylene group, a polyalkylene ether group or the formula -Ar ³ -Y-Ar ⁴ - (in the formula, Ar
³ , Ar ⁴ represents a substituted or unsubstituted arylene group,
Y may be the same or different, and Y represents a single bond, a substituted or unsubstituted alkylene group, a polyalkylene ether group, an alkylidene group, a cycloalkylidene group, an oxygen atom, a sulfur atom, or a vinylene group. )
R ¹ , R ² and R ³ are a substituted or unsubstituted alkyl group,
Represents an aryl group or a halogen atom, l, m and n each independently represents an integer of 0 to 3, and p represents an integer of 5 to 5,000. ] 2. An aromatic polycarbonate resin comprising a structural unit represented by the following formula (Formula 2) and having a number average molecular weight of 2,000 to 400,000 and a weight average molecular weight of 2,500 to 400,000. Embedded image [In the above formula, R ⁴ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, and X represents an alkylene group, a polyalkylene ether group, or the following formula: —Ar ³ —Y—Ar ⁴ —
(Wherein, Ar ³ and Ar ⁴ each represent a substituted or unsubstituted arylene group, which may be the same or different, and Y represents a single bond, a substituted or unsubstituted alkylene group, a polyalkyl ether group, an alkylidene group, A cycloalkylidene group, an oxygen atom, a sulfur atom, or a vinylene group). ] 3. It comprises structural units represented by the following formulas (Chem. 3) and (Chem. 4), and has a number average molecular weight of 2,000 to 400,000 and a weight average molecular weight of 2,500 to 400,000. And the composition ratio of the structural unit is 0 <k / (k +
j) An aromatic polycarbonate resin with ≦ 1. Embedded image Embedded image [In the above formula, Ar ¹ and Ar ² each represent a substituted or unsubstituted aryl group, which may be the same or different. A is a single bond, a substituted or unsubstituted alkylene group, alkylidene group, cycloalkylidene group, an oxygen atom, a sulfur atom, a vinylene group, X is an alkylene group, a polyalkylene ether group or the formula -Ar ³ -Y-Ar ⁴ - (in the formula, Ar
³ , Ar ⁴ represents a substituted or unsubstituted arylene group,
Y may be the same or different, and Y represents a single bond, a substituted or unsubstituted alkylene group, a polyalkylene ether group, an alkylidene group, a cycloalkylidene group, an oxygen atom, a sulfur atom, or a vinylene group. )
R ¹ , R ² and R ³ are a substituted or unsubstituted alkyl group,
Represents an aryl group or a halogen atom, l, m and n each independently represents an integer of 0 to 3, k represents an integer of 5 to 5,000, and j represents an integer of 0 to 5,000. ]