JPH01180561A - Photoconductive film and electrophotographic sensitive body formed by using said film - Google Patents

Abstract

PURPOSE:To obtain a photoconductive film having high sensitivity by incorporating a specific hexaazo compd. therein. CONSTITUTION:At least one kind of the hexaazo compd. expressed by the formula I is incorporated into the above-mentioned film. In the formula I, A denotes the formula II, etc.; R1, R2 denote a hydrogen atom, lower alkyl group, etc.; Z denotes a substd. or unsubstd. methylene group, substd. or unsubstd. imino group, etc.; Ar1-Ar4 respectively denote a substd. or unsubstd. hydrocarbon or hetero system arom. cyclic group or bivalent residual org. group. In the formula II, R denotes a hydrogen atom, lower alkyl group, etc. The photoconductive film having the high sensitivity and the electrophotographic sensitive body formed by using said film are thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photoconductive coating containing a novel organic photoconductive compound and an electrophotographic photoreceptor using the same.

``Prior art and its problems 1 Electrophotographic photoreceptors are widely known to have a photosensitive layer containing as a main component an inorganic photoconductive compound such as hirene, 111 lead oxide, or cadmium sulfide. However, these are not always satisfactory in terms of properties such as thermal stability and durability, and furthermore, they have problems in production and handling due to their toxicity.

On the other hand, electrophotographic photoreceptors having a photosensitive layer containing an organic photoconductive compound as one component are relatively easy to manufacture, inexpensive, easy to handle, and generally contain selenium. It has attracted attention in recent years because it has many advantages such as superior thermal stability compared to photoreceptors. Such I-1 photoconductive compounds include:
Poly-N-vinylcarbazole is the best known, and 2.4.

Electrophotographic photoreceptors having a photosensitive layer containing as a main component an electrooil transfer complex formed from a Lewis acid such as 7-dolinitrile and 9-fluorene have been put to practical use.

In addition, the charge generation function and the transport function of the optical 5tJ electric material are divided into separate materials, respectively. Photographic photoreceptors are known, such as electrophotographic photoreceptors that have a photosensitive layer consisting of a "load generation layer" made of an amorphous selenium film and a charge transport layer containing poly-N-vinylcarbazole as a main component. has already been put into practical use.

Furthermore, attempts have been made to use organic photoconductive compounds as both the charge generating substance and the charge transporting substance in electrophotographic photoreceptors having the functionally separated type sensitive layer mentioned above. In this case, known charge generating substances include azo dyes, phthalocyanine dyes, an1-laquinone dyes, perylene dyes, cyanine dyes, deapyrylium dyes, and squareium dyes. Further, as charge transport substances, amine derivatives, oxazole derivatives, oxadiazole derivatives, triphenylmethane derivatives, etc. are known.

These charge-generating substances J3 and σ charge-transporting substances may be used in various stone agents and 4 if they do not themselves have film-forming ability.
71, and a film is formed thereby. Then, a layer having a charge generating substance and a layer having an electrolyte transporting substance are laminated on a conductive support to form an electron η true value light body, or a charge generating substance and a charge transporting substance. An electrophotographic photoreceptor is known which is formed by forming a layer containing a dispersed state of .

However, compared to those using inorganic photoconductive compounds, electrophotographic photoreceptors that use organic photoconductive compounds as charge-generating substances still suffer from less photoconductive electric shock and have poor durability. However, the current situation is that there are very few that can be put to practical use because they are inferior.

An object of the present invention is to provide a highly sensitive photoconductive coating by employing a novel organic photoconductive compound and an electronic 7J photoreceptor using the same.

[Means for Solving the Problems] The photoconductive film according to the present invention is characterized by containing at least one type of hekylyazo compound represented by the following general formula (I).

, and R represents an organic residue such as a lower alkyl group, an aryl group, an al]xycarbonyloxycarbonyl group, an acyl), or an organic residue. X represents an atomic group necessary for condensing with a benzene ring to form a substituted or unsubstituted hydrocarbon or heteroaromatic ring.

represents. R may be the same and each R1.R2 may be a hydrogen atom, a lower alkyl group, an aryl group, an alkyloxycarbonyl Lt, /lyloxycarbonyl atom, or a monovalent Z represents an organic residue. Z represents a substituted or unsubstituted methylene group, a substituted or unsubstituted imino group, a sulfur atom, a base material, or a selenium atom.

Ar+, Arz, Ar3, Ar. ＋ kiirere iNlIi1! Alternatively, it represents an unsubstituted hydrocarbon-based or -wood-based Waka TM group, or a divalent organic residue. A
rt to Ar4 may be the same or different.

) Further, the electrophotographic photoreceptor according to the present invention has the above-mentioned general formula (I)-C'' on a conductive support.
It is characterized by providing a photosensitive layer having a photoconductive coating containing at least one type of saazo compound.

Until now, there has been no attempt to use the heliolyazo compound represented by the general formula (I) as a photoconductive compound for electrophotography, and the present inventors have proposed to use this compound as a photoconductive compound for electrophotography, particularly It was discovered that an electrophotographic photoreceptor having an excellent sensitivity exceeding 1.1 can be obtained by using a charge-generating material, and the present invention was completed.

Specific examples of compounds represented by the 1fiV formula (1) include:
Examples include:

In the above formula (II), R+, R2, Ar+' ~
Examples of silk combinations of Ar4' are shown in Table 1 attached below.

Examples of Δ in the above formula (I) are shown in Table 2 attached below.

[In formula (1■), R+, Ar゛+ ' ”□△r4
An example of the combination of ' is attached below (=J) in Table 3.

In the formula L (V), the example of A is not shown in Table 4 attached later,
.

Examples of combinations of Ar1' to Δr4' in the above formula (Vl) are shown in Table 5 attached later.

In the above formula (VI), examples of A are not shown in Table 6 attached later.

In the above formula (■), examples of combinations of Ar+' to Ar4' are shown in Table 7 attached later.

Examples of A in the above formula (IX) are shown in Table 8 attached hereto.

The compound represented by -69,r,t: (T) is
For example, as shown in FIG.
Wear.

In addition, in FIG. 7, the symbols in the formula are the general yt:
It has the same meaning as February in (T). These corresponding 1-no-1-lyamino compounds are diazotized with sodium nitrite and hydrochloric acid, and coupled with a coupler such as aniline or α-naph1-lamine in an acidic environment.

In this way, the triamino compound obtained in -) is further nitrited with tri-11 and hydrochloric acid, or with sodium nitrite and Itj?
It is diazotized by f acid, and then converted to 1il by coupling with a thick f1heal AS coupler in a 7 alkali solution.

The electrophotographic photoreceptor of the present invention uses, as a charge-generating substance, a photosensitive compound that is oxidized at the binding margin (T), and can have, for example, the following configuration.

As shown in FIG. 1 or FIG. 2, a V4 layer is formed on a conductive support 1, comprising a charge generation layer 2 containing a charge generation substance as a main component and a charge transport layer 3 containing a charge transport substance as a main component. A photosensitive layer 4 is provided on the body J. Figure 1 shows ``Load generation F?'' 22
There is an example Q in which a charge transport layer 3 is provided on the charge transport layer 3, and FIG. 2 shows an example in which the charge generation layer 2 is provided on the charge transport layer 3.

As shown in FIG. 3 or 4, a photosensitive layer 4 similar to that described in F is provided on a conductive support 1 via an intermediate layer 5.

As shown in FIG. 5 or 6, a photosensitive layer 4 consisting of a layer 6 containing a charge transport material as a main component and a charge generating material 7 dispersed therein is formed on a conductive support 1. It is provided directly or via the intermediate layer 5.

The conductive support 1 may be coated with a metal base, a conductive polymer, a conductive compound such as indium oxide, or a thin film of metal such as aluminum, palladium, gold, etc. used.

The charge generating layer 2 is made by forming the charge generating substance indicated by the above-mentioned binding margin (i) into fine particles in a dispersion medium using a ball mill, homo mixer, sand mill, colloid mill, etc., and mixing and dispersing it with a binder as necessary. Apply a blue dispersion, or apply a solution obtained by dissolving the nine charge-generating substances in a binder in a solvent, using a method such as dipping, spraying, or spraying. It can be formed by

In this case, examples of the binder include phenol resin, polynisder resin, vinyl acetate resin, and polycarbonate resin.
Resin, polyethylene oxide resin, cellulose resin, polyvinylpyrrolidone, polyethylene oxide, polyvinyl chloride resin, starch, polygonyl alcohol, 7-acrylic copolymer resin, methacrylic copolymer resin, silicone resin , polyacrylonitrile symbiotic resin, polyacrylamide, polyvinyl alcohol, etc. can be used.

Note that the charge generation layer 2 can also be formed by converting the compound represented by the general formula (I) into II by a method such as vacuum evaporation.

The charge transport layer 3 can be formed by dispersing or dissolving a charge transport substance in a binder similar to the above and applying the same. In the present invention, the charge transport substance is not particularly limited, but includes, for example, amine derivatives, Axazole+iA 4-body,
AV tadiazole derivatives, trinonylmethane derivatives, etc. are used.

The intermediate layer 5 disposed 1° between the conductive support 1 and the photosensitive layer 4 provides a flash 11 function and an adhesive function, and is made of, for example, casein, polyvinyl alcohol,
Nido 1-1 cellulose, ■-Brenno 1 acrylic acid copolymer, polyamide (Buy[1-6, Bouylon 66, Nylon 610, co-ΦNi 1-1, alkoxymethylated Ni[1], etc.), polyurethane, gelatin , aluminum oxide 4c, etc. can be formed.

Further, the photosensitive layer 4 is formed by dispersing a charge-generating substance 7 in the form of particulates in a layer 6 containing a charge-transporting substance as a main component. It can be formed by dissolving and applying a liquid in which a charge generating substance is dispersed.

〔Example〕

Examples 1 to 16 A solution in which a butyral resin doublet part was dissolved in a 100-fold suspension of isobutyral resin, and a five-fold suspension of 10 types of hel-sazo compounds listed in the table below were ground using a ball mill. was added and dispersed to prepare 16 types of coating solutions. Then, the 8-coat solution was applied onto a 501 N plate using a doctor blade so that the film thickness after drying was 0.3 utn, and dried to form a charge generation layer.

Next, 5 parts by weight of a hydrazone compound represented by the structural formula below and 5 parts by weight of polyvinylcarbazole were dissolved in 70 parts by weight of monochlorobenzene, and this was placed on the charge generation layer to a film thickness after drying. It was coated using a doctor blade to give a concentration of 20 μR and dried to form a C charge transport layer.

The 16 types of electrophotographic photoreceptors obtained in this way were tested using an electrostatic charging tester (manufactured by Rosseki, EPA-81).
00 type), apply a corona charge at 16 KV using a static force method, and then observe the fade marks for 5 seconds. II L, Terujo 1
Photoelectric properties were evaluated by observing photoreduction by exposure at 5+11X for 5 seconds. The first light zone SM potential (v
o), sensitivity (E172), and residual potential (vR) are shown in Table 9.

Below is the blank space in Table 9. However, the sensitivity is shown as ○ = good, Δ - Shintsu, and × - bad.

〔Effect of the invention〕

As explained above, according to the present invention, the binding margin (I)
By using the novel hexaazo compound represented by the following formula, it is possible to obtain a photosensitive coating having high photoconductivity and an electrophotographic photoreceptor using the same. Also, -
By using the novel hexaazo compound represented by the binding margin (I), an electrophotographic photoreceptor with good characteristics can be obtained using the resulting highly sensitive photoconductive coating. Therefore, the present invention can be widely applied to electrophotographic copiers, laser beam printers, LED printers, CRT printers, or other electrophotographic applications in general.

Below margin

[Brief explanation of the drawing]

Figures 1, 2, 3, 4, 5 d3 and 6
The figures are sectional views showing different specific examples of the layer structure of the electrophotographic photoreceptor according to the present invention, and FIG. 7 is a diagram showing a reaction formula for synthesizing the hegisazo compound used in the present invention.

Claims (1)

[Claims] (1) A photoconductive film characterized by containing at least one type of hexaazo compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , where R is a hydrogen atom, lower alkyl group, aryl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, halogen atom, or monovalent organic residue. X represents an atomic group necessary to form a substituted or unsubstituted hydrocarbon or heteroaromatic ring by condensation with a benzene ring Y has ▲mathematical formula, chemical formula, table, etc.▼ or ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ Represents. R's may be the same or different. Further, R_1 and R_2 represent a hydrogen atom, a lower alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a halogen atom, or a monovalent organic residue. Z represents a substituted or unsubstituted methylene group, a substituted or unsubstituted imino group, a sulfur atom, an oxygen atom, or a selenium atom. Ar_1, Ar_2, Ar_3, and Ar_4 each represent a substituted or unsubstituted hydrocarbon-based or heteroaromatic ring group, or a divalent organic residue. Ar_1～Ar_
4 may be the same or different. )(2) An electrophotographic photoreceptor comprising a photosensitive layer having a photoconductive film containing at least one type of hexaazo compound represented by the following general formula (I) on a conductive support. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a hydrogen atom, lower alkyl group, aryl group, alkoxycarbonyl group, aryloxycarbonyl group, Represents an acyl group, a halogen atom, or a monovalent organic residue. There are ▲mathematical formulas, chemical formulas, tables, etc.▼ or ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼ Represents. R's may be the same or different. Furthermore, R_1 and R_2 represent a hydrogen atom, a lower alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a halogen atom, or a monovalent organic residue. Z represents a substituted or unsubstituted methylene group, a substituted or unsubstituted imino group, a sulfur atom, an oxygen atom, or a selenium atom. Ar_1, Ar_2, Ar_3, and Ar_4 each represent a substituted or unsubstituted hydrocarbon-based or heteroaromatic ring group, or a divalent organic residue. Ar_1～Ar_4
may be the same or different. )