JPS60146247A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve sensitivity, durability, etc., by using a specified hydrazone compd. for a photosensitive layer. CONSTITUTION:A layer formed on a conductive substrate incorporates a hydrazone compd. represented by the formula shown here in which R1 is optionally substd. alkyl, alkenyl, or aralkyl; R2 is H, or optionally substd. alkyl, aralkyl, or aryl; R3 is optionally substd. alkyl, alkenyl, or aralkyl; and (n) is 0 or 1. Said compd. is synthesized by heating a ketone compd. together with a pyridylhydrazine compd. in a molar ratio of 1:1 in an alcoholic type solvent, and it is combined with an org. pigment to form a functionally separated type photosensitive body.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor, and more specifically, the present invention relates to an electrophotographic photoreceptor containing an electrophotographic photoreceptor containing a hydrazone compound represented by the following general formula [I] in a layer formed on a conductive support. It relates to photographic photoreceptors.

1S (In the formula, 1 is an alkyl group, alkenyl group, or aralkyl group which may have a substituent, R2 is a hydrogen atom,
Alkyl group, aralkyl group that may have a substituent,
Aryl foundation, FL5 represents an alkyl group, an alkenyl group, an aralkyl group which may have a substituent,
n represents O or 1. ) In conventional electrophotographic technology, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been widely used in the photosensitive layer of electrophotographic photoreceptors, but in recent years organic photoconductive materials have been used in electrophotography. Many studies have been conducted on using it as a photoreceptor.

By the way, the following are the basic properties of photoreceptors used in electrophotography. In other words, (1) the charge is highly charged against corona discharge in the dark (2) there is little leakage (dark decay) of the charge due to the obtained corona band in the dark (3) the charge can be charged by irradiation with light (4) There is little residual charge after light irradiation.

Conventional photoreceptors such as inorganic selenium and cadmium sulfide have basic properties that meet the requirements for photoreceptors. However, these materials have manufacturing problems, such as difficulty in film formation, lack flexibility, and are prone to crystallization.

In addition, it is highly toxic and has restrictions on handling and disposal, and is also a problem in terms of pollution, so the development of new photosensitive materials is desired.

However, in view of these points, research into electrophotographic photoconductors made of organic materials has been actively conducted in recent years, and electrophotographic photoreceptors using various organic compounds have been proposed and put into practical use. There are some things. Generally speaking, compared to inorganic materials, organic materials have better transparency, are lighter in weight,9 have better film-forming properties, and have better flexibility, and can be applied to photoreceptors using appropriate sensitization methods. It has advantages such as easy design.

By the way, typical organic electrophotographic photoreceptors currently being proposed include polyvinylcarbazole and its derivatives, but these do not necessarily have sufficient film properties, flexibility, or adhesive properties. , and polyvinylcarbazole sensitized with pyrylium salt dye (% Kosho 4
8-25658), polyvinyl carbacy/l/,!
:2,4.7-) The one sensitized with linitrofluorenone (U.S. Patent No. 3,484,237) has been improved, but it does not have the basic properties required for a photoreceptor listed above. , mechanical strength, high durability, and other requirements have not yet been obtained.

As a result of extensive research, the present inventors have developed a new organic photoconductor that satisfies all of the above requirements, resulting in the present invention.

In the compound represented by the above general formula (1) according to the present invention, the substituent R1 is an alkyl group which may have a substituent (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a chloromethyl group). group, bromoethyl group,
Methoxymethyl group, ethoxyethyl group, phenoxyethyl group, hydroxyethyl group, methcarboxyethyl group,
(ethocarboxyethyl group, cyanoethyl group, etc.), alkenyl group (e.g. allyl group, 2-butenyl group, 3-butenyl group, β-methallyl group, cinnamyl group, etc.), aralkyl group (e.g. benzyl group, β-phenylethyl group) ,
Naphthylmethyl group, o, m, p-methylbenzyl group, O
, m, p-chlorobenzyl group, 0-, In-, p-
Methoxybenzyl group, 2,4-dimethylbenzyl group, 4
- Represents an ethylbenzyl group, 2-pyridylmethyl group, 4-pyridylmethyl group, etc.

R2 is a hydrogen atom, an alkyl group that may have a substituent (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Chloromethyl group, bromoethyl group, methoxyethyl group,
phenoxyethyl group, etc.), aralkyl group (e.g. benzyl group, phenethyl group, -naphthylmethyl group, o-,
m-, p-methylbenzyl group, 01n11 p-chlorobenzyl group, o-, m-, p-methoxybenzyl group, 4
-methoxyphenylethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, O'-+ m-, p-)
(lyl group, xylyl group, o-2m-, p-chlorophenyl group, o-, m-, p-methoxyphenyl group, etc.). R3 is an alkyl group that may have a substituent (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group,
butyl group, inbutyl group, chloroethyl group, methoxyethyl group, methoxymethyl group, phenoxy7ethyl group, etc.)
, alkenyl groups (e.g. allyl group, 2-butenyl group, 3
-butenyl group, β-methallyl group, cinnamyl group, etc.),
Aralkyl groups (e.g. benzyl group, β-phenethyl group,
naphthylmethyl group, 0-9m-, p-methylbenzyl group, o-, m-, p-chlorobenzyl group, 0 + m+p
-methoxybenzyl group, 2,4-dimethylbenzyl group,
4-ethylbenzyl group, 2-pyridylmethyl group, 4-pyridylmethyl group, etc.). n is an integer of O or 1.

These hydrazone compounds represented by the general formula [1] can be produced by the following method. That is, R2 (It) [IID 1 1 mole of the ketone compound represented by the formula [11] and 1 mole of the pyridylhydrazine compound represented by the formula [■] are first heated in an alcoholic solvent to form [[V ) A hydrazone compound of the formula is obtained. This compound [■] and [■
The desired hydrazone compound [1'l] can be obtained by reacting 1 mole of the halogenated alkyl compound represented by the formula in a suitable solvent. General organic solvents can be used as the solvent in this case,
For example, aromatic hydrocarbons such as benzene, toluene, xylene, and monochlorobenzene, ethers such as tetrahydrofuran, dioxane, and inglovir ether, aprotic solvents such as acetone, dimethylformamide, and dimethyl sulfoxide, and in some cases, water. Proton solvents such as, methanol, and ethanol can also be used. In addition, it is desirable to remove an appropriate alkaline catalyst for this condensation reaction, and examples of alkaline catalysts include sodium hydroxide, potassium hydroxide, temporary sodium acid,
Examples include potassium carbonate, triethylamine, piperidine, and sodium methylate.

Next, synthesis examples of specific compounds will be shown.

Synthesis Example 1 Ethylation of 3-formyl-ethyl-rubazole (2+-pyridylhydrazone (Exemplary Compound (1)) 3-
To 3.29 (0.01 mol) of formyl-ethylcarbazole(2)-pyridylhydrazone were added 2 ml of 5N sodium hydroxide and 30 ml of dimethyl sulfoxide, and with stirring, 1 ml of ethyl iodide was added.
．． 69 (0.01 mol) was added 7 times.

Stir at room temperature and collect the precipitated crystals. After washing with water and recrystallizing from ethyl acetate, 3.3 pale yellow peritectics with a melting point of 156°C were obtained.
Get 2.

Synthesis Example 2 Allylation of 3-formyl-N-ethylcarno(zole-(2)-pyridylhydrazone (Exemplary Compound (4)) In the same manner as described in Synthesis Example 1, allyl bromide 1.29 ( 0.01 mol) to give 2.02 yellow crystals with a melting point of 141°C.

The hydrazone compound-ef11 corresponding to general formula [1] is as follows. However, the present invention is not limited to these compounds.

2H5 2H5 1 2H5 C2) (5 H3 C3H7(n) 2H5 The screw photoreceptor of the present invention has excellent performance by containing one or more of the above-mentioned compounds in the photosensitive layer. has.

Various methods can be applied to use these hydrazone compounds as electrophotographic photoreceptors. For example, the present hydrazone compound and a sensitizing dye may be dissolved or dispersed in a binder, with the addition of a chemical sensitizer or a peep-attracting compound if necessary, and then provided on a conductive support. In the form of a photoreceptor consisting of a photoconductor, or a laminated structure consisting of a carrier generation layer with high charge carrier generation efficiency and a carrier transfer layer, a sensitizing dye or a pigment is provided on a sensitizing support. A photoreceptor, etc., is formed by providing the present hydrazone compound as a carrier transport layer on a carrier generation layer, which is dissolved or dispersed in a binder with the addition of a chemical sensitizer or an electron-withdrawing compound if necessary. However, it can be applied in either case.

More specifically, when producing a photoreceptor using this compound, metal plates, conductively treated paper, conductively treated glass films, metal N'c films, metals, etc. Cylinder, metal vapor deposition or gold F on the surface
A photosensitive layer is formed on a support such as a plastic cylinder which has been processed with foil using a solvent together with a skin 11 negative forming binder.

In this case, sensitizing IW, mechanically curved bullets, sensitizers, and additive substances as described later may be added to improve adhesion and durability.

Skin) i (The following can be used as a forming binder.

Polystyrene resin, styrene-butadiene copolymer resin, polyvinyl acetal resin, diallyl phthalate resin, silicone resin, polysulfone resin, polycarbonate a resin, acrylic resin, methacrylic resin, vinyl acetate resin, acetic acid-crotonic acid copolymer resin, polyphenylene These include oxide resin, polyester resin, alkyd hatsumode, polyarylate resin, styrene-maleic anhydride copolymer resin, styrene-maleic anhydride hafester resin, phenol resin, butyral resin, poval resin, etc., and these can be used alone or as copolymers. As the polymer, one type or a mixture of two or more types can be used. In addition, the use of these binders is in a weight ratio of 0.1 to 0.1 to the weight of the organic photoconductor.
It is added at a rate of 10 times, but preferably in the range of 0.2 to 5 times.

Spectral sensitizing dyes added to improve the sensitivity of the photoreceptor include triphenylmethane dyes such as methyl violet, crystal violet, ethyl violet, Victoria blue, and night blue; erythrosine; Xanthen dyes such as Rhodamine B1 Acridine Red B, Acridine Orange 2G.

Acridine dyes such as Acridine Orange R1 Flaveosin, methylene blue, methylene green,
There are thiazine dyes such as methyl violet, oxazine dyes such as fog blue and melt rub, other cyanine dyes, pyrylium salts, thiapyrylium salts, and photo-conductive dyes with high charge carrier generation efficiency. Pigments include phthalonanine pigments such as metal phthalocyanine and metal-free phthalocyanine, perylene d1 materials such as perylene imide and perylene acid anhydride, other quinacridone pigments, anthraquinone pigments, and azo pigments such as monoazo pigments, bisazo pigments, and trisazo pigments.

In addition to the sensitizers mentioned above, chemical sensitizers may also be added for the purpose of increasing sensitization.

Examples of this chemical sensitizer include p-chlorophenol,
m-chlorophenol, p-nitrophenol, 4-chloro-m-cresol, p-chlorobenzoylacetanilide, N,N'-diethylbarbylic acid, N,N'
-diethylthioparpi=A[,3-(β-oxyethyl)-2-phenylimino-thiazolidone, malonic acid dianilide, 3°3', 5.5'-tetrachloromalonic acid dianilide, a-naphthol, p- Examples include nitrobenzoic acid.

Further, certain electron-withdrawing compounds can be added as sensitizers that combine with the hydrazone compound of the present invention to form a charge transfer complex and exhibit a sensitizing effect. Examples of this substance include 1-chloroanthraquinoi, i-nitroanthraquinone, 2,3-dichloro-naphthoquinone, 3.
3'-Dinitrobenzophenone, 4-nitrobenzalmalononitrile, phthalic anhydride, 3-(α-cyano-p
-nitrobenzal) phthalide, 2,4.7-trinitrofluorenone, 1-methyl-4-nitrofluorenone, 2,7-sinitro-3,6-dimethylfluorenone, and the like.

Other additives to the photoreceptor, such as plasticizers, antioxidants, and ultraviolet absorbers, can be added to the photoreceptor if necessary.

Depending on the form of the photoreceptor, the present hydrazone compound is mixed with the various additives mentioned above and mixed with a solvent. Manufacture.

Most organic solvents can be used as coating solvents. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and monochlorobenzene, halogenated hydrogen such as chloroform, dichloroethane, trichloroethylene, and methylene chloride, needles such as dioxane, tetrahydrofuran, and trioxane, ethyl acetate,
Use solvents such as esters such as propyl acetate, butyl acetate, methyl cellosolve acetate, alcohols such as ethyl alcohol, clovil alcohol, butyl alcohol, cyclohexanol, methyl cellosolve, etc. alone or as a mixed solvent of two or more. If necessary, mether ethyl lactone, methyl isobutyl ketone, N,
N-dimethylformamide, acetonitrile, etc. can be further added and used.

Next, examples of the present invention will be shown, but the present invention is not limited thereto.

Examples: ε-type copper phthalocyanine pigment purified for electrophotography (manufactured by Toyo Ink Co., Ltd.) 10 F, butyral resin (manufactured by Union Carbide Co., Ltd.) 10 F, xylene 15 orff: kneaded in a ball mill for 6 hours, and the resulting dispersion was mixed with S - Using a doctor, a film with a dry film thickness of 75-. A charge generation layer was prepared by applying the coating to a thickness of 0.4 μm.

Next, one part of the compound of the present invention and a polycarbonate resin (
Mitsubishi Gas Chemical Co., Ltd. Kneepilon N-6) 1 ply, the sewn part was dissolved in dichloroethane to make it 10% by weight, and a solution was applied onto the above-mentioned load generation layer using an S-doctor to give a dry film thickness of 10μ. I coated it in such a way that it had a "turtle movement" effect.

The electrophotographic properties of the composite electrophotographic photoreceptor thus obtained were evaluated using an electrostatic recording paper tester (Kawaguchi Denki Co., Ltd., model SP-428). In the measurement, the photoreceptor was charged with a corona charge of 16 KV, and the surface potential at that time was set as ■0.
The surface potential after starvation for 10 seconds was defined as VjO. V1
0/Vo was expressed as a darkening rate. /i & degree is light half-decrease exposure amount) determined in Sirilux seconds. The results are shown in Table 1.

Table 1 Example 2 Aluminum plate (thickness 100/j) which was grained and then anodized
& Created a light body.

A car material with the following structure was used as the low load generating substance.

1 part by weight of the above pigment and styrene-maleic anhydride Hafestel copolymer resin (acid value 15o) were mixed in a mixed solvent of toluene and butyl acetate (1:1) at a concentration of 5% by weight, and then placed in a ball mill for 5 hours. Dispersed. This dispersion is S-
The charge generation layer was applied using a doctor and dried to form a charge generation layer having a thickness of about 0.3 μm.

Next, one part of compound 2H5 having the following structure according to the present invention and a styrene-acrylic acid copolymer resin (acid value 1
80) 1.5 parts by weight of monochlorbenze/KIO was dissolved to give a weight percent of monoclobenze/KIO, and this was coated on the above-mentioned carrier raw layer to form a charge transfer layer with a dry film thickness of about 7 μm. .

In response to the white light from the photoreceptor obtained in this way, an image of 1'4! When exposure was performed, a normal good toner image could be obtained. Next, this toner image was immersed in an etching solution (402 parts of monoethanolamine, 35 parts of benzyl alcohol, 22 parts of sodium hexametalate, 282 parts of potassium hydroxide, and water added to make a total of 1.It). By removing one quadrant, a printing master plate was obtained. When this master plate was subjected to cam pulling treatment and printed on an offset printing machine, a printed image with good reproduction that exceeded that of a single print was obtained.

Claims (1)

[Claims] (1) An electrophotographic photoreceptor comprising a layer containing a compound represented by the following general formula [1] on a conductive support. Old 3 (in the formula, 1 mo 1 is an alkyl group which may have a substituent,
Alkenyl group, aralkyl group, 2 represents a hydrogen atom, an alkyl group that may contain a substituent, an aralkyl group, an aryl group, I (3 represents an alkyl group, an alkenyl group that may have a substituent) , represents an aralgyl group, and n represents O or 1.)