JPH093023A - Benzofluorene compound and its production - Google Patents

Abstract

PURPOSE: To obtain the subject new compound capable of being charged into a suitable electric potential and little in discharge in a dark place, capable of rapidly discharging the electric potential under the irradiation of light, useful as a photoconductive raw material, especially an electric charge-transfer substance, and suitable for the photosensitive layers of electronic photographic sensitizers. CONSTITUTION: A compound of formula I [R is a (substituted) 1-8C alkyl; X is a 1-6C alkyl, a halogen, a 1-6C alkoxycarbonyl, cyano, nitro; (n) is 0-3]. For example, 1-(1,4-diethoxycarbonyl-2,3-benzofluorenylideneamino)-2-isopropylbenzene. The compound of formula I is obtained by reacting a compound of formula II with a compound of formula III in the presence of an acidic catalyst such as (trifluoro)acetic acid or titanium tetrachloride.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel benzofluorene compound and a method for producing the same, and more particularly to a benzofluorene compound useful as a photoconductive material, particularly as a charge transport material, and a method for producing the same.

[0002]

2. Description of the Related Art In an electrophotographic process, generally, a photoconductive photosensitive member is first uniformly charged in a dark place by, for example, corona discharge, and then imagewise exposure is performed to selectively discharge electric charges in an exposed portion. This is an image forming method in which an electrostatic latent image is formed, and the electrostatic latent image is visualized using toner or the like to form a visible image. The basic characteristics required for such an electrophotographic photosensitive member are (1) being able to be charged to an appropriate potential in a dark place, (2) being less discharged in a dark place, and (3) being rapidly exposed to light. Examples include discharging. Conventionally, an electrophotographic photoreceptor using an inorganic photoconductive substance such as selenium, a selenium-tellurium alloy, or selenium-arsenic has been adopted to satisfy these characteristics, and has been used in many copying machines and the like. However, these inorganic photoconductive substances have environmental problems such as toxicity,
Also, since it is used in an amorphous state, for example, heat,
It is difficult to handle because it is easily crystallized due to dirt or the like and its characteristics are deteriorated. Moreover, it is necessary to perform vacuum evaporation to a film thickness of several tens of μm, resulting in high cost.

Therefore, recently, research on an electrophotographic photosensitive member using an organic photoconductive substance has progressed, and a part thereof has been put to practical use. Most of the organic electrophotographic photoconductors that have been put into practical use have a function-separated photosensitive layer that uses a charge generating substance and a charge transporting substance. Examples of the charge transporting substance include stilbene derivatives (special Kaisho 58-
198425, JP-A-58-189145), triphenylamine derivatives (JP-A-58-65).
No. 440), a fluorenylidene methane compound (JP-A-60-69657),
Naphthalenedicarboxylic acid imide compound (JP-A-5-25
Many compounds such as acceptor compounds such as JP-A-136) are known.

[0004]

However, an organic electrophotographic photoreceptor using a conventional charge transport material, particularly an organic electrophotographic photoreceptor using an acceptor compound as a charge transport material, is required for the electrophotographic photoreceptor. However, in reality, no charge-transporting substance capable of sufficiently satisfying such properties has been found. Therefore, an object of the present invention is to provide a novel benzofluorene compound useful as a photoconductive material, particularly a charge transporting material, and a method for producing the same.

[0005]

The above object of the present invention can be achieved by a benzofluorene compound represented by the following general formula (1).

Embedded image (In the formula, R is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxycarbonyl group having 1 to 6 carbon atoms, a cyano group or a nitro group. It represents a selected group and may be the same or different. N represents an integer of 0 to 3.) The above object of the present invention is to provide a benzofluorenone compound represented by the following general formula (2) and the following general formula: This is achieved by a method for producing a benzofluorene compound represented by the above general formula (1), which comprises reacting an aniline compound represented by the formula (3) under an acidic catalyst.

Embedded image (In the formula, R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.)

Embedded image (In the formula, X represents a group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxycarbonyl group having 1 to 6 carbon atoms, a cyano group and a nitro group, and n represents an integer of 0 to 3 When n is 2 or 3, X may be the same or different.)

The novel benzofluorene compound according to the present invention is extremely useful as a photoconductive material, especially as a photoconductive material in an electrophotographic photoreceptor, and is optically or chemically treated with a sensitizer such as a dye or a Lewis acid. To be sensitized.
Further, it is particularly useful as a charge transporting substance in a so-called function-separated type electrophotographic photosensitive member using an organic pigment or an inorganic pigment as a charge generating substance.

Examples of the sensitizer include triallylmethane dyes such as methyl violet and crystal violet, xanthene dyes such as rose bengal, erythrosine and rhodamine B, and thiazine dyes such as methylene blue.
2,4,7-trinitro-9-fluorenone may be mentioned. When the benzofluorene compound of the present invention is used as a charge transporting substance in a function-separated electrophotographic photosensitive member, examples of the charge generating substance used with it include:
CI Pigment Blue 25 (C.I. 2118
0), CI Pigment Red 41 (CI.212)
00), CI Basic Red 3 (C.I. 452)
Azo pigments such as 10), CI Pigment Blue 16
(C.I.74100) and other phthalocyanine-based pigments, CIVAT BROWN 5 (C.I.73410), CIVAT Die (C.I.73030) and other indigo-based pigments, Argos Scarlet B, and Indense Scarlet R And organic pigments such as perylene pigments, and inorganic pigments such as selenium, selenium-tellurium alloys, cadmium sulfide, and α-silicon.

The benzofluorene compound of the present invention is not only useful as a photoconductive material for electrophotography and a charge transport material in a function-separated type electrophotographic photoreceptor, but also as an electronic device such as a solar cell and an organic EL element. It can also be used in the field and exhibits excellent properties.

Examples of the substituent in the alkyl group of the general formula (1) include a phenyl group, a halogen atom such as a fluorine atom and a chlorine atom, and an alkoxy group such as a methoxy group and an ethoxy group. Among the benzofluorene compounds represented by the general formula (1), in particular, R is an alkyl group having 1 to 4 carbon atoms or a fluorine-substituted product thereof, or X is an alkyl group having 2 to 4 carbon atoms, 1 to 4 carbon atoms
The alkoxycarbonyl group or cyano group can be suitably used because it has excellent compatibility with the binder resin such as the electrophotographic photosensitive layer.

Specific examples of the benzofluorene compound represented by the general formula (1) of the present invention are shown in Tables 1 to 1-4, but the invention is not limited thereto.

[0011]

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

The benzofluorene compound represented by the above general formula (1) of the present invention is obtained by reacting a benzofluorene compound (2) with an aniline compound (3) under an acidic catalyst, for example, according to the following reaction step (A). It can be manufactured by Reaction step (A) (In the formula, R is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxycarbonyl group having 1 to 6 carbon atoms, a cyano group or a nitro group. Represents a selected group, and n represents an integer of 0 to 3. When n is 2 or 3, X may be the same or different.)

In this case, examples of the acidic catalyst used include organic acids such as acetic acid, trifluoroacetic acid, or trifluoroborate, and acidic inorganic substances such as zinc chloride, iron chloride, titanium tetrachloride, or aluminum chloride. You can As the reaction solvent, a halogen-based solvent such as methylene chloride, chloroform, or 1,2-dichloroethane, carbon disulfide, or an aromatic solvent such as chlorobenzene or nitrobenzene can be used, but a solvent may not be used. As the reaction solvent, 0 ° C to 150 ° C
C is preferable, and 0 ° C. to 100 ° C. is particularly preferable.

[0014]

The present invention will be described more specifically with reference to the following examples. Parts here are by weight.

Example 1 (Exemplified Compound N in Table 1 above)
o. Synthesis of 6) 1,4-diethoxyarbonyl-2,3-benzo-9-
3.47 g of fluorenone was added to 150 ml of methylene chloride, and 5.69 g of titanium tetrachloride was added dropwise thereto over 10 minutes while stirring under ice cooling. Next, under the same conditions, 8.11 g of 2-isopropylaniline was added dropwise over 1 hour, and the reaction was performed for 3 hours under the same conditions. After the reaction, the reaction mixture was poured onto ice and extracted with 1,2-dichloroethane. Next, the 1,2-dichloroethane solution is washed twice with water,
After drying over anhydrous magnesium sulfate, 1,2-dichloroethane was distilled off, and the residue was subjected to column chromatography using toluene as a developing solvent, and the resulting crude target product was mixed with an ethanol-ethyl acetate mixed solvent. Was recrystallized to obtain 3.58 g of a pure target product. The melting point and elemental analysis results are shown in Table 2. The infrared absorption spectrum of this compound is shown in FIG.

Example 2 (Exemplified Compound N in Table 1 above)
o. Synthesis of 16) In the same manner as in Example 1, except that 3.54 g of 2-cyanoaniline was used instead of 2-isopropylaniline in Example 1, the target product was obtained. The melting point and elemental analysis results are shown in Table 2. The infrared absorption spectrum of this compound is shown in FIG.
The melting point and elemental analysis results are shown in Table 2. The infrared absorption spectrum of this compound is shown in FIG.

Examples 3 to 5 Instead of 1,4-diethoxycarbonyl-2,3-benzo-9-fluorenone of Example 1, 1,4-dibutoxycarbonyl-2,3-benzo-9-fluorenone. ,
1,4-di (2,2,2-trifluoroethoxycarbonyl) -2,3-benzo-9-fluorenone, 1,4-
Di (2-ethoxycarbonyl) -2,3-benzo-9-
In the same manner as in Example 1, except that various aniline compounds were used instead of fluorenone and 2-isopropylaniline, the exemplified compound No. 30, No. 54, No.
65 was obtained. The melting point and elemental analysis results are shown in Table 2.

[0018]

[Table 2]

Application Example 1 5 parts of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.)
Disperse 5 parts of polyvinyl butyral resin (S-Rex BLS: Sekisui Chemical Co., Ltd.) and 90 parts of tetrahydrofuran in a ball mill for 12 hours, and add 2 parts of tetrahydrofuran.
A coating liquid was prepared by adding again so that the concentration of the dispersion liquid would be wt% and redispersing. This coating solution was vapor-deposited with aluminum 10
Cast film is coated on a 0 μm thick polyester film with a doctor blade and dried, and the film thickness after drying is 0.5 μm.
Was formed. Next, 6 parts of the benzofluorene compound of the present invention (Exemplified Compound No. 16 in Table 1),
Polycarbonate resin (K-1300: Teijin Chemicals)
A coating solution having a formulation consisting of 10 parts and 94 parts of tetrahydrofuran was prepared, and the coating solution was cast-coated on the charge generation layer with a doctor blade and dried to give a film thickness of 2 after drying.
A 0 μm-thick charge transport layer was formed to prepare a laminated electrophotographic photoreceptor formed of aluminum electrode / charge generation layer / charge transport layer.

The electrophotographic photosensitive member obtained as described above was subjected to +6 Kv corona charging using an electrostatic copying paper tester (EPA-8200: manufactured by Kawaguchi Denki Seisakusho), and after being positively charged, 20 Leave for a second in the dark, measure the surface potential V ₀ (V) at that time, and then irradiate with a halogen lamp so that the surface illuminance is 40 lux,
The half-exposure amount E1 / 2 (lux · sec) was measured. As a result, V ₀ was 1490 V and E1 / 2 was 28.0 lux.
sec.

[0021]

INDUSTRIAL APPLICABILITY The benzofluorene compound of the present invention is useful as a photoconductive material, particularly as a charge transport material, and when used in the photosensitive layer of an electrophotographic photosensitive member, it has the basic characteristics required for the electrophotographic photosensitive member. It can be fully satisfied.

[Brief description of drawings]

1 is an infrared absorption spectrum diagram of a benzofluorene compound (Exemplified Compound No. 6 in Table 1) obtained in Example 1. FIG.

2 is an infrared absorption spectrum diagram of a benzofluorene compound (Exemplified Compound No. 16 in Table 1) obtained in Example 2. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03G 5/06 314 G03G 5/06 314Z // C07B 61/00 300 C07B 61/00 300

Claims (2)

[Claims] 1. A benzofluorene compound represented by the following general formula. Embedded image (In the formula, R is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxycarbonyl group having 1 to 6 carbon atoms, a cyano group or a nitro group. Represents a selected group, and n represents an integer of 0 to 3. When n is 2 or 3, X may be the same or different.) 2. The general formula (1) according to claim 1, wherein the benzofluorenone compound represented by the following general formula (2) and the aniline compound represented by the following general formula (3) are reacted under an acidic catalyst. A method for producing a benzofluorene compound represented by 1). Embedded image (In the formula, R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.) (In the formula, X represents a group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxycarbonyl group having 1 to 6 carbon atoms, a cyano group and a nitro group, and n represents an integer of 0 to 3 When n is 2 or 3, X may be the same or different.)