JP3141303B2 - N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine derivative useful as an organic photoconductor and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as an organic photoconductive material of a photoreceptor used in an electrophotographic system, for example, poly-N
-Vinyl carbazole, triphenylamine compound (US Pat. No. 3,180,730), benzidine compound (US Pat. No. 3,265,496, JP-B-39-115)
46, JP-A-53-27033).
-N, N, N ',
N'-tetraphenyl-m-phenylenediamine (U.S. Pat. No. 3,265,496), N, N, N ', N'-
Many proposals have been made, such as a tetra-substituted phenyl-m-phenylenediamine compound (JP-A-1-142462).

[0003] The "electrophotographic method" as used herein generally means that a photoconductive photoreceptor is first charged in a dark place by, for example, corona discharge, and then imagewise exposed to selectively charge the exposed portion. An electrostatic latent image is obtained by discharging
Further, this is one of the image forming methods in which the latent image portion is visualized by a developing unit using toner or the like to form an image. The basic characteristics required of the photoreceptor in such an electrophotographic system include: 1) being charged to an appropriate potential in a dark place, 2) being less discharged in a dark place, and 3) being irradiated with light. 4) that the photosensitive layer does not undergo layer separation, crystallization, etc.
That a uniform layer is maintained.

However, the conventional photoconductive organic materials do not always satisfy these requirements.

[0005]

SUMMARY OF THE INVENTION The present invention satisfies all basic electrophotographic characteristics and is useful as a photoconductive material.
It is an object of the present invention to provide a novel N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine derivative and a method for producing the same.

[0006]

According to the present invention, there is provided the following:

Embedded image (R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group, and may be the same or different.) N-phenyl-
An N- (3-diphenylaminophenyl) -1-pyrenylamine derivative is provided.

Embedded image (R ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted phenyl group. A) an N-phenyl-N- (3-aminophenyl) -1-pyrenylamine derivative represented by the following formula:

Embedded image (R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group. X represents a bromine atom or an iodine atom.) Characterized by reacting with a fluorinated benzene derivative

Embedded image (R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group, and may be the same or different.) N-phenyl-
A method for producing an N- (3-diphenylaminophenyl) -1-pyrenylamine derivative is provided.

As described above, the N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine derivative represented by the above formula 1 of the present invention is a useful and novel compound as a photoconductive material, This compound is produced by reacting the corresponding N-phenyl-N- (3-aminophenyl) -1-pyrenylamine derivative represented by the above formula with the corresponding halogenated benzene derivative represented by the above formula. be able to.

[0008] N-phenyl-N-
By reacting the (3-aminophenyl) -1-pyrenylamine derivative with the halogenated benzene derivative represented by the above formula 3, N-phenyl-N represented by the above formula 1 is obtained.
In order to produce the-(3-diphenylaminophenyl) -1-pyrenylamine derivative, the raw material mixture is mixed with copper powder, copper oxide, copper halide, or the like, in a quantity sufficient to neutralize hydrogen halide generated during the condensation reaction. A large amount of an alkaline substance, in the presence or absence of a solvent, under a nitrogen atmosphere,
It can be produced by reacting at a temperature of about 150 to 250 ° C.

In this case, examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. As the reaction solvent, nitrobenzene, dichlorobenzene, quinoline,
N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned.

Specific examples of R ¹ and R ² in the chemical formulas ¹ , 2 and 3 of the pyrenylamine derivative represented by the chemical formula 1 and the starting compounds represented by the chemical formulas 2 and 3 of the present invention are as follows. Examples of the alkyl group for R ² include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group;
As the alkoxy group, a methoxy group, an ethoxy group,
And lower alkoxy groups such as propoxy groups. Further, as a substituent in the alkyl group, a phenyl group,
Examples include a halogen atom, an alkoxy group, an aryloxy group, and the like. Examples of the substituent in the phenyl group include a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group), and a lower alkoxy group (eg, a methoxy group). Groups, ethoxy groups, propoxy groups, etc.) and halogen atoms (eg, bromine, chlorine, fluorine).

The N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine derivative represented by the above formula 1 of the present invention is extremely useful as a photoconductive material in an electrophotographic photoreceptor, It is sensitized optically or chemically by a sensitizer such as a dye or Lewis acid. Further, this is particularly useful as a charge transporting substance in a so-called function-separated type photoreceptor using an organic pigment or an inorganic pigment as a charge generating substance.

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

The organic pigments include CI Pigment Blue 25 (CI No. 21180), CI Pigment Red 41 (CI No. 21200), and CI Pigment Red 31 (CI No. 45210).
Pigments such as azo pigments such as C.I.
No. Phthalocyanine pigments such as C.I. 74100), indigo pigments such as C.I. Is mentioned. Also,
Inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide, and α-silicon can also be used.

[0014]

【Example】

Example 1 N- (3-aminophenyl) -N- (4-methylphenyl) -1-pyrenylamine 2.79 g (7.00 mmol)
1), 15.3 g (70.0 mmol) of 4-iodotoluene
l), potassium carbonate (3.87 g) and copper powder (0.44 g) were azeotropically dehydrated in an ester tube under a stream of nitrogen in the range of 209-2.
Stirred at 12 ° C. for 10 hours. After allowing to cool to room temperature, the mixture was filtered using celite, chloroform was added to the filtrate, the chloroform layer was washed with water, dried over magnesium sulfate, and further concentrated under reduced pressure to obtain a dark brown oil. This was treated with a silica gel column [eluent, mixed solvent of toluene / n-hexane (1: 3)], and recrystallized from a mixed solvent of 1,4-dioxane / ethanol. 1.81 g (yield 44.7%) of N- (4-methylphenyl) -N- [3-bis (4-methylphenyl) aminophenyl] -1-pyrenylamine was obtained. Melting point was 190.0-191.0 ° C. Elemental analysis: C ₄₃
It was as follows as H ₃₄ N _2. C% H% N% Found 89.17 5.74 4.76 Calculated 89.24 5.92 4.84

Embedded image FIG. 1 shows the infrared absorption spectrum (KBr tablet method) of this compound.

Examples 2,3,4,5,6 N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine shown in Table 1 in the same manner as in Example 1 using the corresponding starting compounds The derivative was obtained. Table 1 shows the melting points and elemental analysis values of each main compound.

[0016]

[Table 1]

Application Example As a charge generating substance,

Embedded image 7.5 parts of a bisazo compound represented by the following formula and 500 parts of a 0.5% tetrahydrofuran solution of a polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) were pulverized and mixed in a ball mill, and the obtained dispersion was applied to an aluminum-evaporated polyester film. Was applied with a doctor blade and dried naturally to form a charge generation layer having a thickness of about 1 μm. Next, a polycarbonate resin [Panelite K-1300 manufactured by Teijin Limited] 1
Part of the compound obtained in Example 1 as a charge transport material was dissolved in a resin solution of 8 parts of tetrahydrofuran and 8 parts of tetrahydrofuran, and the solution was applied on the charge generation layer with a doctor blade,
The resultant was dried at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes to form a charge transport layer having a thickness of about 20 μm. Next, in order to examine the sensitivity in the visible region of the thus-obtained laminated electrophotographic photosensitive member A, an electrostatic copying paper test apparatus (SP428, manufactured by Kawaguchi Electric Works, Ltd.) was used for this photosensitive member in a dark place. Then, the surface potential Vm (v) of the photoreceptor was measured after charging by performing a corona discharge of -6 KV for 20 seconds, and the surface potential Vo (v) was measured after being left in a dark place for further 20 seconds. Next, a tungsten lamp light is irradiated so that the illuminance on the photoreceptor surface becomes 4.5 lux, and Vo becomes 1
The exposure amount E1 / 2 (lux · sec) until the value became 1/2 and the residual surface potential Vr (v) after irradiation for 30 seconds were measured. Table 2 shows the results.

[Table 2]

[0018]

According to the present invention, the novel N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine derivative represented by the above formula 1 functions effectively as a photoconductive material as described above. Also, since it is optically or chemically sensitized by a sensitizer such as a dye or a Lewis acid, it is suitably used as a charge transporting material for a photosensitive layer of an electrophotographic photoreceptor. It is useful as a charge transport material in a so-called function-separated type photosensitive layer in which a transport layer is divided into two layers. Further, the novel N-phenyl-N- (3-diphenylaminophenyl) -1-pyrenylamine derivative can be produced by the production method of the present invention.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of N- (4-methylphenyl) -N- [3-bis (4-methylphenyl) aminophenyl] -1-pyrenylamine of the present invention obtained in Example 1 (KBr tablet method). )

FIG. 2 shows the N- (phenyl) of the present invention obtained in Example 6.
-N- [3-diphenylaminophenyl] -1-pyrenylamine infrared absorption spectrum (KBr tablet method)

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroshi Adachi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (56) References JP-A-5-88389 (JP, A) JP-A Sho 53-27033 (JP, A) JP-A-1-142462 (JP, A) JP-B-39-11546 (JP, B1) US Patent 3,180,730 (US, A) US Patent 3,265,496 (US, A) (58) Search ⁷ (Int. Cl. ⁷ , DB name) C07C 211/61 C07C 209/10 C07C 213/02 C07C 217/92 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] [Claim 1] (R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group, and may be the same or different.) N-phenyl-
N- (3-diphenylaminophenyl) -1-pyrenylamine derivatives. 2. The following chemical formula 2 (R ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted phenyl group. )) And an N-phenyl-N- (3-aminophenyl) -1-pyrenylamine derivative represented by the following formula: (R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group. X represents a bromine atom or an iodine atom.) Wherein the compound is reacted with a fluorinated benzene derivative. (R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenyl group, and may be the same or different.) N-phenyl-
A method for producing an N- (3-diphenylaminophenyl) -1-pyrenylamine derivative.