JPH05105638A - New distyryl compound and photosensitive material containing the same - Google Patents

Abstract

PURPOSE:To provide a new distyryl compound usable as a charge-transfer material of photosensitive material or electroluminescente element. CONSTITUTION:The compound of formula I [Ar1 and Ar2 are H, aikyl or (substituted)aryl; Ar2 and Ar4 are (substituted)aryl, (substituted)condensed ring group or (substituted)heterocyclic group; R1 and R2 are H, alkyl, alkoxy or halogen; (n) and (m) are 0 or 1], e.g. the compound of formula II. The compound can be produced by reacting a phosphorus compound of formula III [X is trialkyl or triarylphosphonium group of formula P-(R3)3Y or dialkyl or diarylphosphite group of formula PO(OR4)2; Y is halogen; R3 and R4 are alkyl or aryll with a ketone compound of formula IV and formula V. The compound has the activity of a charge-transfer substance to transfer charged carrier generated by the absorption of light in extremely high transfer efficiency, exhibits remarkable contribution especially to the charge mobility and gives a photo- sensitive material having excellent quick response.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compound having a distyryl structure. The distyryl compound can be used as a light-sensitive material, and more specifically, can be used as a charge-transporting material for a photoreceptor or an electroluminescence device.

[0002]

2. Description of the Related Art Conventionally, various organic compounds usable as a light-sensitive material or a charge-transporting material are known, such as anthracene derivative, anthraquinone derivative, imidazole derivative, carbazole derivative and styryl derivative.
Japanese Patent Application Laid-Open No. 2-56559 discloses the following general formula:

[Chemical 3] A styryl compound represented by the formula [wherein R _{1 to} R ₂ , X _{1 to} X ₄ and n represent those described in the above publication] is disclosed.

However, the above-mentioned materials are basically required to have excellent photosensitivity or charge transportability when applied to, for example, a photoconductor, but further compatibility with other members and durability are required. However, weather resistance and the like are also required, and in reality, there are few materials that satisfy such characteristics.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel distyryl compound which is different from any of the structures described above. Another object of the present invention is to provide a photoreceptor using the novel distyryl compound. Another object of the present invention is to provide an electroluminescent device using the novel distyryl compound in a charge transport layer.

[0005]

The present invention has the following general formula:
[I]:

[Chemical 4] A distyryl compound represented by The distyryl compound of the present invention has a biphenyl structure at the center, 2-,
It has a structural characteristic that it has a vinyl group at the 2'-ortho position and is excellent in charge transportability, solubility and ozone resistance.

In the general formula [I], Ar ₁ and Ar ₃ each represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, or an aryl group such as a phenyl group. The aryl group may have a substituent such as a disubstituted amino group, a heterocyclic group or an aryl group. Ar ₂ and Ar ₄ may independently have an aryl group, for example, a phenyl group, a naphthyl group, etc., a condensed cyclic group, for example, anthracene, pyrene, fluorene, etc., or a heterocyclic group, for example, the following: formula:

[Chemical 5] Etc. These groups may have a substituent such as a disubstituted amino group, a heterocyclic group or an aryl group. A
At least one of r ₂ and Ar ₄ is preferably an aryl group. n and m represent an integer of 0 or 1.

R ₁ and R ₂ are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group, a halogen atom (a fluorine atom, a chlorine atom). , Bromine atom, etc.). An alkyl group is preferred from the viewpoint of compatibility with the resin.

Specific examples of the compound having a distyryl structure represented by the general formula [I] include those having the following structural formula.

[Chemical 6]

[0009]

[Chemical 7]

[0010]

[Chemical 8]

[0011]

[Chemical 9]

[0012]

[Chemical 10]

[0013]

[Chemical 11]

[0014]

[Chemical 12]

[0015]

[Chemical 13]

In the above compound examples, [2], [4], [5],
[6], [7], [8], [9], [11], [15], [18],
[19], [23], [27], [32], [33], and [36] are
Particularly preferred.

The distyryl compound represented by the general formula [I] is, for example, the following general formula [II]:

[Chemical 14] [Wherein R ₁ , R ₂ , n and m have the same meanings as in formula [I], and X is a trialkyl group or a triarylphosphonium group represented by —P— (R ₃ ) ₃ Y, or PO (OR ₄ ) ₂ represents a dialkyl or diaryl phosphite group; wherein Y represents a halogen atom, and R ₃ and R ₄ each represent an alkyl group or an aryl group. ] And a phosphorus compound represented by the following general formulas [III] and [IV];

[Chemical 15] [In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ have the same meanings as those in the formula [I]. ] It can synthesize | combine by making it react with the ketone compound represented by this. The phosphorus compound represented by the general formula [II] used in the synthesis of the present invention can be easily produced by heating the corresponding compound and trialkyl phosphite directly or in a solvent such as toluene or xylene. it can. Trialkyl phosphite has 1 to 4 carbon atoms
And an alkyl group, especially a methyl group and an ethyl group are preferable. The phosphorus compound represented by the general formula [II] thus obtained and the aldehyde compound represented by the general formula [III] are reacted at room temperature to a temperature of about 100 ⁰ C in the presence of a basic catalyst. Let As the solvent in the reaction, for example, hydrocarbons, alcohols and ethers are preferable, and methanol, ethanol, isopropanol, butanol,
2-methoxyethanol, 1,2-dimethoxyethane,
Examples thereof include bis (2-methoxyethyl) ether, dioxane, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, N, N-dimethylformamide, N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone. Of these, polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide are preferable. As the basic catalyst (condensation agent), an alcoholate such as caustic soda, caustic potash, sodium amide, sodium hydrogen and sodium methylate, and potassium t-butoxide is used. The reaction temperature is about ^{0 0 C~} about 10
It can be selected from a wide range up to 0 ⁰ C. Preferably from ¹⁰ 0 Celsius to about 80 ⁰ C.

These distyryl compounds may be used alone or in combination. It is also possible to use it as a mixture with another charge transport material, for example, a hydrazone compound. The distyryl compound represented by the general formula [I] has excellent photosensitivity and charge transportability, can be used very effectively as a photoconductive material, and is particularly excellent in charge transportability.

The distyryl compound represented by the general formula [I] of the present invention can be used as a light-sensitive material for a photoconductor, particularly as a charge-transporting substance. Further, it can be used for the charge transport layer of an electroluminescence device by utilizing its charge transport property.

First, the case where the distyryl compound represented by the general formula [I] is used as a charge transport material for a photoconductor will be described. Various types of photoconductors are known as photoconductors, and the distyryl compound of the present invention can be applied to any form of the photoconductor. For example, a single-layer photoconductor in which a charge generation material and a photosensitive layer in which a charge transport material is dispersed in a binder resin are provided on a support, or a charge generation layer containing a charge generation material as a main component on a support are used. There is a so-called laminated type photoconductor in which a charge transport layer is provided on the photoconductor. One or more distyryl compounds of the present invention are used as a charge transport material. The distyryl compound acts as a charge transport material,
The charge carriers generated by absorbing light can be transported extremely efficiently. In particular, it is possible to make a photoreceptor that contributes significantly to the improvement of charge mobility and is excellent in high-speed response.

Further, since the distyryl compound of the present invention has excellent ozone resistance and light stability, a photoreceptor having excellent durability can be obtained. Furthermore, the distyryl compound of the present invention has good compatibility with the binder resin and is less likely to precipitate crystals, which contributes to improvement in sensitivity and repeatability.

As the charge generating material, a bisazo pigment,
Triarylmethane dye, thiazine dye, oxazine dye, xanthene dye, cyanine dye, styryl dye, pyrylium dye, azo pigment, quinacridone pigment, indigo pigment, perylene pigment, polycyclic quinone pigment , Bisbenzimidazole-based pigments, indusulon-based pigments, squalium salt-based pigments, azulene-based pigments, phthalocyanine-based pigments and other organic substances, selenium, selenium / tellurium, selenium / arsenic and other selenium alloys, cadmium sulfide, cadmium selenide Inorganic substances such as zinc oxide and amorphous silicon. Other than this, any material can be used as long as it absorbs light and generates charge carriers with an extremely high probability.

Examples of suitable binder resins include, but are not limited to, saturated polyester resins, polyamide resins, acrylic resins, ethylene-vinyl acetate resins, ionically cross-linked olefin copolymers (ionomers), styrene. −
Thermoplastic resins such as butadiene block copolymer, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin, urethane resin, silicone resin, phenol resin, melamine resin, xylene resin, alkyd resin , Thermosetting resins such as thermosetting acrylic resins; photocurable resins; photoconductive resins such as polyvinylcarbazole, polyvinylpyrene, polyvinylanthracene, and polyvinylpyrrole. These can be used alone or in combination. These electrically insulating resins are individually measured to be 1 × 10
It is desirable to have a volume resistance of ¹² Ω · cm or more.

In order to prepare a single-layer type photoreceptor, fine particles of a charge generating material are dispersed in a resin solution or a solution in which a charge transporting material and a resin are dissolved, and this is coated and dried on a conductive support. Good. At this time, the thickness of the photosensitive layer is 3 to 3
The thickness is 0 μm, preferably 5 to 20 μm. If the amount of the charge generating material used is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor, or the mechanical strength of the photosensitive layer will be weakened. On the other hand, the range is 0.01 to 2 parts by weight, preferably 0.2 to 1.2 parts by weight. The distyryl compound represented by the general formula [I] as the charge transport material is 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 1 part by weight of the binder resin. It is 0.2 to 1.2 parts by weight. 0.
When the amount is less than 01 parts by weight, the sensitivity is poor, and when the amount is more than 2 parts by weight, the film formability is poor and the mechanical strength of the photosensitive layer is weakened.

In order to prepare a laminated type photoreceptor, a charge generating material is vacuum-deposited on a conductive support, or is dissolved in an appropriate solvent and applied, or a pigment is added in an appropriate solvent or necessary. For example, it can be obtained by coating and drying a coating solution prepared by dispersing it in a solution in which a binder resin is dissolved, and then coating and drying a solution containing a charge transport material and a binder resin thereon. At this time, the thickness of the charge generation layer is 4 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer is 3 to 50.
μm, preferably 5 to 30 μm. The ratio of the charge transport material in the charge transport layer is 0.2 to 1 part by weight of the binder resin.
2 parts by weight, preferably 0.3 to 1.3 parts by weight.

The photoreceptor of the present invention comprises a binder resin, a plasticizer such as halogenated paraffin, polychlorinated biphenyls, dimethylnaphthalene, dibutyl phthalate and O-terphenyl, chloranil, tetracyanoethylene, 2,4,7.
-Trinitrofluorenone, 5,6-dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride, electron withdrawing sensitizer such as 3,5-dinitrobenzoic acid, methyl violet, rhodamine B, cyanine dye, pyrylium salt A sensitizer such as thiapyrylium salt may be used. As the electrically insulating binder resin used in the present invention, a known electrically insulating thermoplastic resin or a binder such as a thermosetting resin, a photocurable resin or a photoconductive resin can be used. .. As the conductive support used in the photoreceptor of the present invention, a foil or plate of copper, aluminum, silver, iron, nickel or the like in a sheet shape or a drum shape is used, or these metals are used as a plastic film. Vacuum-deposited, electroless plated, conductive polymer, indium oxide, etc.
A layer in which a conductive compound layer such as tin oxide is provided by coating or vapor deposition on a support such as paper or a plastic film is also used.

An example of the constitution of a photoconductor using the distyryl compound of the present invention is schematically shown in FIGS. Figure 1 shows the substrate
A photoreceptor having a photosensitive layer (4) comprising a charge generation material (3) and a charge transport material (2) mixed with a binder on the (1), wherein the distyryl compound of the present invention is used as the charge transport material. Has been. FIG. 2 shows a function separation type photoreceptor having a charge generation layer (6) and a charge transport layer (5) as a photosensitive layer.
The charge transport layer (5) is formed on the surface of (6). The distyryl compound of the present invention is incorporated in the charge transport layer (5). Similar to FIG. 2, FIG. 3 shows a function-separated type photoreceptor having a charge generation layer (6) and a charge transport layer (5). Contrary to FIG. 2, charges are formed on the surface of the charge transport layer (5). A generation layer (6) is formed. FIG. 4 shows a surface protective layer on the surface of the photoreceptor of FIG.
(7) is provided, and the photosensitive layer (4) is a charge generation layer (6).
And a function-separated type photoreceptor having a charge transport layer (5). FIG. 5 shows an intermediate layer between the substrate (1) and the photosensitive layer (4).
(8) is provided, and the intermediate layer (8) has improved adhesiveness,
It can be provided in order to improve the coating property, protect the substrate, and improve the charge injection property from the substrate to the photosensitive layer.

Suitable materials for the intermediate layer are polyimide, polyamide, nitrocellulose, polyvinyl butyral, polyvinyl alcohol, aluminum oxide and the like, and the film thickness is preferably 1 μm or less.

The distyryl compound represented by the general formula [I] of the present invention can be applied to the charge transport layer of an electroluminescence device by utilizing its charge transport property. The case where the distyryl compound of the present invention is applied to the charge transport layer of an electroluminescent device will be described below.

The organic electroluminescent element is composed of at least an organic light emitting layer and a charge transport layer containing a distyryl compound between electrodes. FIG. 6 schematically shows a cross section of the electroluminescent element. In the figure, (11) is an anode on which a charge transport layer (12) and an organic light emitting layer (1
3) and the cathode (14) are sequentially laminated, and the charge transport layer contains the distyryl compound represented by the above general formula [I]. By applying a voltage to the anode (11) and the cathode (14), the organic light emitting layer (13) develops color.

Anode of organic electroluminescent device
As the conductive substance used as (11), those having a work function larger than 4 eV are preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc,
Tungsten, silver, tin, gold etc. and their alloys,
Tin oxide and indium oxide are used. The metal forming the cathode 14 preferably has a work function smaller than 4 eV, and magnesium, calcium, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, and alloys thereof are used.

In the organic electroluminescence device, at least the anode (11) or the cathode (14) is a transparent electrode so that light emission can be seen. At this time, if a transparent electrode is used for the cathode, the transparency is likely to be impaired, so the anode is preferably a transparent electrode. When the transparent electrode is formed, the conductive material as described above may be formed on the transparent substrate by means of vapor deposition, sputtering or the like so as to ensure a desired light-transmitting property. As a transparent substrate, it has an appropriate strength, and when manufacturing an electroluminescence element,
It is not particularly limited as long as it is transparent and is not adversely affected by heat due to vapor deposition and the like, and examples thereof include a glass substrate, a transparent resin such as polyethylene, polypropylene, polyether sulfone, and polyether ether ketone. It is also possible to use. Commercially available products such as ITO and NESA are known as those having a transparent electrode formed on a glass substrate, and these may be used.

The charge transport layer (12) has the above-mentioned general formula [I].
It may be formed by vapor deposition of the distyryl compound represented by, or may be formed by spin coating an appropriate solution or resin solution of the distyryl compound. When formed by a vapor deposition method, its thickness is usually 0.01 to 0.3 μm, and when formed by a spin coating method, the content of the distyryl compound is about 20 to 500% by weight with respect to the binder resin. So that the thickness is about 0.05 to 1.0 μm.

An organic light emitting layer is formed on the charge transport layer 12 thus formed. As the organic light-emitting body used in the organic light-emitting layer, known ones can be used. For example, epidrizine, 2,5-bis [5,7-di-t-pentyl-2-benzoxazolyl] thiophene, 2,2′- (1,
4-phenylenedivinylene) bisbenzothiazole, 2,
2 '-(4,4'-biphenylene) bisbenzothiazole,
5-methyl-2- {2- [4- (5-methyl-2-benzoxazolyl) phenyl] vinyl} benzoxazole, 2,
5-bis (5-methyl-2-benzoxazolyl) thiophene, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, perinone, 1,4-diphenylbutadiene, tetraphenylbutadiene, coumarin,
Macridine stilbene, 2- (4-biphenyl) -6-phenylbenzoxazole, aluminum trisoxine, magnesium bisoxine, bis (benzo-8-quinolinol) zinc, bis (2-methyl-8quinolinolato) aluminum oxide, indium tris Oxine, aluminum tris (5-methyloxine), lithium oxine, gallium trioxine, calcium bis
(5-chlorooxine), polyzinc-bis (8-hydroxy-5-quinolinonyl) methane) dilithium epinedridione, zinc bisoxine, 1,2-phthaloperinone, 1,
2-naphthaloperinone etc. can be mentioned. In addition, general fluorescent dyes such as fluorescent coumarin dyes, fluorescent perylene dyes, fluorescent pyran dyes, fluorescent thiopyran dyes,
A fluorescent polymethine dye, a fluorescent merocyanine dye, a fluorescent imidazole dye and the like can also be used. Among these, a chelated oxinoid compound is particularly preferable. The organic light-emitting layer may have a single-layer structure of the above-mentioned light-emitting substance, or in order to adjust characteristics such as emission color and emission intensity,
It may have a multilayer structure. Next, the above-mentioned cathode is formed on the organic light emitting layer.

As described above, the charge transport layer (12) on the anode (11),
The case where the light emitting layer (13) and the cathode (14) are sequentially laminated to form an organic luminescence element has been described.
A light emitting layer (13), a charge transport layer (12) and an anode may be sequentially laminated on (14).

A pair of transparent electrodes is formed by connecting a suitable lead wire (15) such as a nichrome wire, a gold wire, a copper wire or a platinum wire to each electrode.
The organic luminescence element emits light by applying an appropriate voltage (Vs) to both electrodes.

The organic electroluminescent element of the present invention can be applied to various display devices, display devices and the like. The present invention will be described below with reference to specific examples. In the following examples, "part" means
Unless otherwise specified, it means "parts by weight".

Synthesis Example 1 Synthesis of Distyryl Compound [5] A dialdehyde compound [a] represented by the following formula:

[Chemical 16] 5.74 g, a phosphonate compound represented by the following formula [b]:

[Chemical 17] 4.54 g was dissolved in 100 ml of dimethylformamide. While cooling the resulting solution to 5 ^{0 C,} was added dropwise to a suspension containing potassium -t- butoxide 3g in dimethylformamide 100 ml, was stirred at room temperature for 8 hours and left overnight. The obtained mixture was poured into 1 liter of ice water and then neutralized with dilute hydrochloric acid. After about 1 hour, the precipitated crystals were filtered. The filtered product was washed with water and separated and purified by silica gel chromatography using toluene as a developing solvent. The residue obtained by distilling off toluene under reduced pressure was recrystallized and purified from acetonitrile to give 5.3 g of yellow crystals (yield 7
4%) was obtained. The results of elemental analysis are shown in Table 1 below.
(As C ₅₄ H ₄₄ N ₂ ). The obtained infrared absorption spectrum is shown in FIG. 7.

[0039]

[Table 1]

Synthesis Example 2 Synthesis of Distyryl Compound [4] A dialdehyde compound [c] represented by the following formula:

[Chemical 18] 5.46 g, a phosphonate compound represented by the following formula [b]:

[Chemical 19] 4.54 g was dissolved in 100 ml of dimethylformamide. While cooling the resulting solution to 5 ^{0 C,} it was added dropwise over 30 minutes to a suspension containing sodium ethylate 2g The solution in dimethyl formamide 100 ml. The resulting solution was stirred at room temperature for 5 hours and then left overnight. The obtained mixture was poured into 1 liter of ice water and then neutralized with dilute hydrochloric acid. After about 1 hour, the precipitated crystals were filtered. The filtered product was washed with water and separated and purified by silica gel chromatography using toluene as a developing solvent. The residue obtained by distilling off toluene under reduced pressure was recrystallized and purified from acetonitrile to obtain 5.4 g of yellow crystals (yield 78%). The results of elemental analysis are shown in Table 2 below (as C ₅₂ H ₄₀ N ₂ ).
The infrared absorption spectrum of the obtained compound is shown in FIG.

[0041]

[Table 2]

Application of Photoreceptor to Charge Transport Material Example 1 Bisazo compound represented by the following general formula [A]

[Chemical 20] 0.45 parts and 0.45 parts of polyester resin (Vylon 200; manufactured by Toyobo Co., Ltd.) were dispersed in a sand mill together with 50 parts of cyclohexanone. The resulting dispersion of the bisazo compound was dried on aluminized mylar having a thickness of 100 μm using a film applicator to give a dry film thickness of 0.3 g / m 2.
^It was applied so that it would be ^2, and then dried.

On the charge generation layer thus obtained, 50 parts of a distyryl compound [2] and 50 parts of a polycarbonate resin (Panlite K-1300; manufactured by Teijin Chemicals Ltd.) were added.
The solution dissolved in 400 parts of 4-dioxane has a dry film thickness of 1
It was coated to a thickness of 6 μm and dried to form a charge transport layer. Thus, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was obtained.

The thus-obtained photoconductor was used in a commercially available electrophotographic copying machine (Minolta Camera Co .; EP-450Z).
Exposure amount E _1/2 (lux · se) required to halve the initial surface potential V ₀ (V) and the initial potential by corona charging at −6 Kv
c) Attenuation rate DD of initial potential when left in the dark for 1 second
R ₁ (%) was measured.

Examples 2 to 4 have the same structure as in Example 1 except that the distyryl compound [2] used in Example 1 was replaced by the distyryl compounds [4], [5] and [6]. A photoconductor using each of the above was prepared. With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

Example 5 Bisazo compound represented by the following general formula [B]:

[Chemical 21] 0.45 parts, polystyrene resin (molecular weight 40,000) 0.
45 parts together with 50 parts cyclohexanone were dispersed by a sand mill.

The dispersion of the obtained bisazo compound was made to a thickness of 1
A film applicator was used to apply a dry film thickness of 0.3 g / m ² on 00 μm aluminized mylar, and then dried. A solution prepared by dissolving 50 parts of the distyryl compound [7] and 50 parts of a polyarylate resin (U-100; Unitika Ltd.) in 400 parts of 1,4-dioxane on the charge generation layer thus obtained was dried film. It was applied to a thickness of 20 μm and dried to form a charge transport layer.
In this way, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Examples 6 to 8 have the same constitution as in Example 5, but the distyryl compounds [8], [9] and [11] are used instead of the distyryl compound [7] used in Example 5. A photoconductor using each of the above was prepared. With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

Example 9 Polycyclic quinone pigment represented by the following general formula [C]:

[Chemical formula 22] 0.45 parts, polycarbonate resin (Panlite K-1
3000: Teijin Chemicals Ltd.) 0.45 parts dichloroethane 5
It was dispersed by a sand mill together with 0 part. The obtained polycyclic quinone pigment dispersion was applied onto a 100 μm thick aluminized mylar using a film applicator so that the dry film thickness was 0.4 g / m ^2, and then dried. The distyryl compound was formed on the charge generation layer thus obtained.
[15] A solution prepared by dissolving 60 parts and 50 parts of polyarylate resin (U-100; manufactured by Unitika Ltd.) in 400 parts of 1,4-dioxane was applied so as to have a dry film thickness of 18 μm, and dried to transport charges. Layers were formed. In this way, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Examples 10 to 11 Photosensitizers having the same structure and the same method as in Example 9, except that the distyryl compounds [18] and [19] were used instead of the distyryl compounds [15] used in Example 9, respectively. The body was made. With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

Example 12 Perylene pigment represented by the following general formula [D]

[Chemical formula 23] 0.45 parts and 0.45 parts of butyral resin (BX-1; manufactured by Sekisui Chemical Co., Ltd.) were dispersed by a sand mill together with 50 parts of dichloroethane. The obtained dispersion of perylene-based pigment was applied onto aluminized mylar having a thickness of 100 μm using a film applicator so that the dry film thickness was 0.4 g / m ^2, and then dried. 50 parts of the distyryl compound [23] and a polycarbonate resin (PC-Z; manufactured by Mitsubishi Gas Chemical Co., Inc.) on the charge generation layer thus obtained.
A solution of 400 parts of 1,4-dioxane dissolved in 400 parts was applied to a dry film thickness of 18 μm to form a charge transport layer. In this way, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Examples 13 to 14 Photosensitizers having the same constitution as in Example 12 except that the distyryl compounds [27] and [32] are used instead of the distyryl compounds [23] used in Example 12, respectively. The body was made. With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

Example 15 0.45 parts of titanyl phthalocyanine, butyral resin
(BX-1; manufactured by Sekisui Chemical Co., Ltd.) 0.45 parts was dispersed together with 50 parts of dichloroethane by a sand mill. Using a film applicator, the obtained dispersion of phthalocyanine pigment was placed on an aluminized mylar having a thickness of 100 μm.
The coating was applied so that the dry film thickness was 0.3 g / m ^2, and then dried. 50 parts of the distyryl compound [5] and a polycarbonate resin (PC
-Z; manufactured by Mitsubishi Gas Chemical Co., Inc.) 50 parts of 1,4-dioxane 4
A solution dissolved in 00 parts was applied to a dry film thickness of 18 μm to form a charge transport layer. In this way, 2
An electrophotographic photoreceptor having a photosensitive layer composed of layers was produced.

Examples 16 to 17 Photosensitizers having the same structure and the same method as in Example 15, except that the distyryl compounds [26] and [36] are used instead of the distyryl compound [5] used in Example 15, respectively. The body was made. With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

Example 18 50 parts of copper phthalocyanine and 0.2 part of tetranitrocopper phthalocyanine were dissolved in 500 parts of 98% concentrated sulfuric acid with sufficient stirring, and this was poured into 5000 parts of water, and photoconductivity of copper phthalocyanine and tetranitrocopper phthalocyanine. After depositing the material composition, it was filtered, washed with water, and dried at 120 ° C. under reduced pressure. 10 parts of the photoconductive composition thus obtained were used for 22.5 parts of a thermosetting acrylic resin (Acridic A405; manufactured by Dainippon Ink and Chemicals), and melamine resin (Super Beckamine J
820; Dainippon Ink and Chemicals, Inc.) 7.5 parts, distyryl compound
[6] Fifteen parts were placed in a ball mill pot together with 100 parts of a mixed solvent prepared by mixing methyl ethyl ketone and xylene in the same amount and dispersed for 48 hours to prepare a photosensitive coating liquid, which coating liquid was applied onto an aluminum substrate and dried. And thickness is about 15μm
To form a photosensitive layer to prepare a photoreceptor. The photoreceptor thus obtained was subjected to the same method as in Example 1 except that corona charging was performed at +6 Kv, and V ₀ , E _1/2 and DDR ₁ were measured.

Examples 19 to 21 The same method as in Example 18 but having the same constitution, except that the distyryl compound [6] used in Example 18 was replaced by the distyryl compounds [9], [14] and [27]. A photoconductor using each of the above was prepared. Regarding the photoreceptor thus obtained, Example 1
V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 8.

Comparative Examples 1 to 4 Compounds having the same structure and the same method as in Example 18, except that the following compound was used instead of the distyryl compound used in Example 18.
Example 18 except that [E], [F], [G], and [H] are used, respectively.
A photoconductor was prepared in exactly the same manner as in.

[Chemical formula 24] With respect to the thus obtained photoreceptor, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 18.

Comparative Examples 5 to 7 Compounds having the same constitution as in Example 18 except that the distyryl compound [6] used in Example 18 was replaced with the following compounds [I], [J] and [K]. A photoconductor was prepared in exactly the same manner as in Example 18 except that each was used.

[Chemical 25] In Comparative Examples 1 to 7, compounds [E], [G],
Regarding the photosensitive coating liquids using [I] and [K], it was observed that some crystals were precipitated during the coating of the photosensitive layer. The thus obtained photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 15. Examples 1 to 21,
V ₀ which obtained photosensitive member in Comparative Example _{1~7, E 1/2, DDR} 1
The measurement results of are summarized in Tables 3 and 4.

[0059]

[Table 3]

[0060]

[Table 4]

As can be seen from Tables 2 and 3, the photoconductor of the present invention has a sufficient charge holding ability even in the laminated type or the single layer type, and the dark decay rate is small enough to be used as a photoconductor. , Also excellent in sensitivity.

Further, Example 18, Example 19 and Comparative Example 6
For Comparative Example 7, a commercially available electrophotographic copying machine (manufactured by Minolta Camera Co .; EP-350Z) was used, and the surface potential V immediately after initial copying and continuous copying of 10,000 sheets.
₀ (V), sensitivity E _1/2 (lux · sec) and residual potential V
_R (V) was measured. The results are shown in Table 5 below.

[0063]

[Table 5]

[0064]

INDUSTRIAL APPLICABILITY The present invention provides a novel distyryl compound. The distyryl compound provided by the present invention can be used in a charge transport layer of a photoconductor or an electroluminescence device. The photoconductor in which the distyryl compound of the present invention is applied to the charge transport layer has excellent photoconductor characteristics such as sensitivity, charge transportability, initial surface potential, and dark decay rate, and little light fatigue upon repeated use.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a dispersion type photoconductor in which a photosensitive layer is laminated on a conductive support.

FIG. 2 is a schematic cross-sectional view of a function-separated type photoreceptor in which a charge generation layer and a charge transport layer are laminated on a conductive support.

FIG. 3 is a schematic cross-sectional view of a function-separated type photoreceptor in which a charge transport layer and a charge generation layer are laminated on a conductive support.

FIG. 4 is a schematic cross-sectional view of a photoconductor in which a photoconductive layer and a surface protective layer are formed on a conductive support.

FIG. 5 is a schematic cross-sectional view of a photoconductor in which an intermediate layer and a photoconductive layer are formed on a conductive support.

FIG. 6 shows a schematic cross-sectional view of an electroluminescent device.

FIG. 7 is a diagram showing an infrared absorption spectrum of a distyryl compound example of the present invention.

FIG. 8 is a diagram showing an infrared absorption spectrum of a distyryl compound example of the present invention.

[Explanation of symbols]

 1 Base 2 Charge Transport Material 3 Charge Generation Material 4 Photosensitive Layer 5 Charge Transport Layer 6 Charge Generation Layer 7 Surface Protection Layer 8 Intermediate Layer 11 Anode 12 Charge Transport Layer 13 Organic Light Emitting Layer 14 Cathode

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 209/08 9283-4C 209/82 9283-4C 215/06 7019-4C 219/02 6701-4C 223/22 6701-4C C09K 11/06 Z 6917-4H G03G 5/00 8305-2H

Claims (2)

[Claims] 1. The following general formula [I]: [In the formula, Ar ₁ and Ar _{3 each} independently represent a hydrogen atom, an alkyl group, or an aryl group which may have a substituent; Ar ₂ and Ar _{4 each} independently have a substituent. Good, an aryl group, a condensed cyclic group or a heterocyclic group; R ₁ and R ₂ independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; and n and m each represent an integer of 0 or 1. Represents a distyryl compound. 2. On a conductive support, the following general formula [I]: [In the formula, Ar ₁ and Ar _{3 each} independently represent a hydrogen atom, an alkyl group, or an aryl group which may have a substituent; Ar ₂ and Ar _{4 each} independently have a substituent. Good, an aryl group, a condensed cyclic group or a heterocyclic group; R ₁ and R ₂ independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; and n and m each represent an integer of 0 or 1. A photoreceptor having a photosensitive layer containing a distyryl compound represented by