JPH01187569A - Photoconductive film and electrophotographic body formed by using said film - Google Patents

Abstract

PURPOSE:To obtain a high-sensitivity photoconductive film by incorporating a specific hydrazone compd. therein. CONSTITUTION:At least one kind of the compd. expressed by formula I is incorporated into the photoconductive film. In formula I, R1-R5 denote a hydrogen atom, straight or branched alkyl group which is unsubstd. or has a substituent, aryl group which is unsubstd. or has a substituent, aralkyl group which is unsubstd. or has a substituent, aryloxy group; R1-R5 may be the same or different from each other. The high-sensitivity photoconductive film having photoconductivity is 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 a gastric photoreceptor using the same.

(Prior art and its issues) As an electrophotographic photoreceptor, selenium, oxidation! It has been widely known that the photosensitive layer contains lIl lead, cadmium sulfide, and other inorganic photoreactive gold compound components. However, these are not necessarily satisfactory in terms of properties such as thermal stability +1 and durability (.<'K<).Furthermore, they are toxic, so they are manufactured and have problems in handling.

- On the other hand, an electrophotographic photoreceptor having a photosensitive layer containing an organic photoconductive compound as a main component is relatively easy to manufacture;
It has attracted attention in recent years because it has many advantages, such as being inexpensive, easy to handle, and generally having better thermal stability than Relene photoreceptors.

The best known such organic photoconductive compound is poly-N-vinylcarbazole, which is
An electrophotographic photoreceptor having a photosensitive layer containing as a main component a charge transfer complex formed from a Lewis acid such as 4.7-1-nitro-9-7 rheolenone has already been put to practical use.

In addition, the charge generation function and charge transport function of the photoconductor are
Electrophotographic photoreceptors are known that have functionally separated photosensitive layers of a laminated type or a dispersed type in which each layer is divided into separate materials (15), for example, a charge generation layer consisting of an amorphous selenium thin film and a poly-N - Electrophotographic photoreceptor having a photosensitive layer consisting of a charge transport layer containing vinylcarbazole as a main component 7. A true photoreceptor has already been put into practical use 1. Furthermore, an electrophotographic photoreceptor having the following functionally separated photoreceptor layer: Attempts have also been made to use organic photoconductive compounds as both charge-generating substances and charge-transporting substances.In this case, charge-generating substances include azo dyes, phthalocyanine dyes, an-1-hera-4-non dyes, perylene dyes, and cyanine dyes. Known pigments include thiapyrylium pigments, squalium pigments, etc. Also known as charge transport substances include amine derivatives, oxazole derivatives, oxadiazole derivatives, and triphenylmethane derivatives.

When these charge-generating substances and charge-transporting substances do not have the ability to form a film by themselves, they are used in combination with various binders to form a film. Then, an electrophotographic photoreceptor is formed by laminating a layer containing a charge-generating substance and a layer containing a charge-transporting substance in conductive potting soil, or a state in which the charge-generating substance and the charge-transporting substance are dispersed. An electrophotographic photoreceptor having a C-containing layer is known.

However, electrophotographic photoreceptors using organic photoconductive compounds as charge transport materials still have lower photoconductive sensitivity and durability than those using inorganic photoconductive compounds. Currently, there are very few products that can be put to practical use.

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

[Means to solve the problem]

The photoconductive film according to the present invention is characterized by containing at least one type of hydrazone compound represented by the following general formula (T).

(In the formula, R1-R5 are a hydrogen atom, an unsubstituted or substituted linear or branched alkyl group, an unsubstituted or [substituted It])7 lyl group, an unsubstituted or substituted The electrophotographic photoreceptor according to the present invention represents an acyl group, a hydrogen atom, an aru group, or an aryl A4 group which covers the group; , on the conductive support, the general formula (I)
The present invention is characterized by providing a photosensitive layer having a photoconductive coating containing at least one species of a hydrazone compound represented by:

Until now, there has been no attempt to use the hydrazone compound represented by the general formula (I) as a photoconductive compound for electrophotography. The present inventors have discovered that an electrophotographic photoreceptor with excellent sensitivity can be colored by using the same as a compound, and have completed the present invention.

Examples of shells of the compound represented by general formula (1) include the following.

The compound represented by the general formula (I) can be synthesized, for example, according to a known reaction formula as shown in FIG.

The electrophotographic photoreceptor of the present invention uses the hydrazone compound represented by the general formula (I) as a charge transport material, and can have, for example, the following 41-layer structure.

As shown in FIG. 1 or 2, a laminate of an IU charge generation layer containing a charge generation substance as a main component and a charge transport layer 3 containing a charge transport substance as a main component is formed on a conductive support 1. 1-Setting layer 4 (Fig. 1 shows an example in which the charge transport layer 3 is provided on the charge generation layer 2, and Fig. 2 shows a case where the charge transport layer 3 is provided on the top of the charge transport layer 3. This is an example of setting layer 2.

3 or 4), a photosensitive layer 41 is provided on a conductive support 1 via an intermediate layer 5 in the same manner as described below.

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 directly deposited on a conductive support 1. , or provided via the intermediate layer 5.

The conductive support 1 may be a metal plate, or paper or plastic made conductive by coating, vapor depositing, or laminating a conductive compound such as a conductive polymer or indium oxide, or a metal thin film such as aluminum, palladium, or gold. is used.

The charge generation layer 2 is made by forming a charge valve material into fine particles in a dispersion medium using a ball mill, a homomixy "l-, a sand mill, a colloid mill, etc., and mixing and dispersing the material with a binder as necessary to obtain a dispersion liquid. Alternatively, it can be formed by coating a solution obtained by dissolving a charge-generating substance in a binder in a solvent using a method such as a dipping method, a spray method, or a spinner method.

In this case, as the binder, for example, Futonol resin,
Polynisple resin, vinyl acetate resin, polycarbonate resin, polypeptide resin, cellulose resin, polyvinylpyrrolidone, polyethylene oxide, polyvinyl chloride resin, starch, polyvinyl alcohol, acrylic copolymer resin, methacrylic copolymer resin, silicone resin , polyacrylonitrile copolymer resin, polyacrylamide, polyvinyl butyral, etc. can be used.

Note that the charge generation layer 2 can also be formed by forming a charge generation substance into a thin film by a method such as vacuum deposition.

The charge transport layer 3 can be formed by dispersing or dissolving a charge transport substance in a binder similar to that described below and applying the mixture.

In the present invention, the charge generating substance is not particularly limited, but includes, for example, selenium d5, selenium alloys, and CdS.

Inorganic photoconductors such as cdse, cdsse, 2nOJ3 and 7nS, phthalocyanine pigments such as metal phthalocyanines and thermometallic notalocyanines, azo pigments, perylene pigments, indigoid pigments, -1 pucridone pigments,
Polycyclic quinone pigments, cyanine dyes, squalic dyes, indanthrone pigments, xandene dyes, such as poly-N-
Charge transfer complexes consisting of electron-donating substances such as vinylcarbazole and electron-accepting substances such as trinitrofluorenone, eutectic complexes formed from pyrylium salt dyes and polycarbonate resin, azulenium salt dyes J3 and a[rufa] Silicon or the like is used.

The intermediate layer 5 disposed between the conductive support 1 and the photosensitive layer 4 has a barrier function and an adhesive function, and is made of, for example, casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid. Copolymer, polyamide (゛I [-] N6, Nylon 66, Nylon 61
0, copolymerized bouylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc.

Further, the photosensitive layer 4 in which a fine particulate charge generating substance 7 is dispersed in a layer 6 mainly composed of a charge transporting substance is obtained by dispersing or dissolving the charge transporting substance in a binder as described below.
Furthermore, it can be formed by applying a liquid in which a charge generating substance is dispersed.

[Embodiments of the invention]

(Examples 1 to 7) 2 parts by weight of butyral resin and 10 parts by weight of isopropyl alcohol
A coating solution was prepared by adding and dispersing Bisazo Kairi Gotoichibu (not shown below), which was ground in a ball mill, into a solution containing 0 parts by weight. Then, the coating solution was applied onto a 50 μm N plate using a doctor blade so that the film thickness after drying would be 0.3 μm, and dried to form a charge generation layer.

(Bisazo pigment) Next, using 7 types of hydrazone compounds shown in the specific examples, 1 to 5 small R parts of polycarbonate to 5 parts by weight of dojisuphenol were dissolved in 70 parts of t-nochlorobenzene, This was coated on top of the charge generation layer using a doctor blade so that the film thickness after drying would be 20 μm, and dried to form a charge transport layer.

Regarding the seven types of electrophotographic photoreceptors obtained in this way,
Electrostatic charging test device (manufactured by Kawaguchi Electric ■, EPΔ-8100
The photoelectric properties were evaluated by corona charging at 16 KV using a static method using a static method, observing dark decay for 5 seconds, and observing light decay by exposing for 5 seconds at an illuminance of 151 ux. Initial charging potential (Vo) and sensitivity (E1) measured in this way
72), the results of residual potential (vR) are shown in Table 1 below.

Margin below Table 1 However, the sensitivity is shown as ○good, △fair, and ×poor.

〔Effect of the invention〕

As explained above, according to the present invention, by using a novel organic photoconductive compound represented by the general formula (I), a photoconductive film having high sensitivity photoconductivity and an electronic film using the same are produced. A photographic photoreceptor can be obtained. Therefore, the present invention can be widely applied to general electrophotographic application fields such as electrophotographic copying machines, laser beam printers, LED printers, and CRT printers.

[Brief explanation of the drawing]

1, 2, 3, 4, 5, and 6 are cross-sectional views showing different specific examples of layers (-1) of the electrophotographic photoreceptor according to the present invention, and FIG. 1 is a diagram showing a reaction formula for synthesizing a hydrazone compound used in the present invention.

Claims (2)

[Claims] (1) A photoconductive film characterized by containing at least one type of hydrazone compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 to R_5 are hydrogen atoms, unsubstituted or substituent-containing linear or branched alkyl groups, unsubstituted or substituent groups R_1 to R_5 may be the same or different from each other.
▲There are mathematical formulas, chemical formulas, tables, etc. ▼ may form a ring containing N. Furthermore, R_4 may form a ring containing N with ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) (2) An electrophotographic photoreceptor comprising, on a conductive support, a photosensitive layer having a photoconductive film containing at least one hydrazone compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 to R_5 are hydrogen atoms, unsubstituted or substituent-containing linear or branched alkyl groups, unsubstituted or substituent groups R_1 to R_5 may be the same or different from each other.
▲There are mathematical formulas, chemical formulas, tables, etc. ▼ may form a ring containing N. Furthermore, R_4 may form a ring containing N with ▲There are mathematical formulas, chemical formulas, tables, etc.▼. )