JP2665685B2 - Electrophotographic photoreceptor and printing original plate for electrophotographic plate making - Google Patents

Description

The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor having a layer containing a novel charge transporting substance or an electrophotographic photoreceptor having a layer containing a novel photoconductive substance. . The present invention also relates to an electrophotographic printing plate precursor having a layer containing a novel charge transport material.

[Conventional technology]

Conventionally, inorganic photoconductive materials such as selenium, cadmium sulfide, zinc oxide, and amorphous silicon have been used as photoconductive materials for electrophotography. These inorganic photoconductive materials have the advantage of having good electrophotographic properties, i.e. good photoconductivity and charge acceptance and insulation in the dark.
However, the reaction has various disadvantages. For example, high manufacturing costs, pollution problems, lack of flexibility and susceptibility to heat and mechanical shock.

In order to overcome the disadvantages of these inorganic photoconductive materials in recent years,
Electrophotographic photoreceptors using organic photoconductive materials have been actively studied and many proposals have been made.

As the organic electrophotographic photoreceptor, a laminated photoreceptor having at least two layers on a conductive support, that is, a charge generation layer that generates charge carriers by exposure and a charge transport layer that transports charge carriers, is mainly used. The charge transport layer basically consists of a charge transport material that is generated in the charge generation layer and transports charge carriers injected into the charge transport layer, and a resin binder.

The properties required of the charge transport material include (a) that the charge generating material efficiently transmits light absorbed by the charge generating agent in order to efficiently generate charges, (b) sufficient charge, and (c) And the ability to efficiently inject and quickly transport charge carriers generated by the charge generating substance.

On the other hand, as a lithographic offset printing plate, a PS plate using a positive type photosensitive agent mainly containing a diazo compound and a phenol resin or a negative type photosensitive agent mainly containing an acrylic monomer or a prepolymer has been put to practical use. However, since all of these methods have low sensitivity, a plate master on which an image has been recorded in advance is subjected to close contact exposure to perform plate making. In recent years, due to advances in computer image processing, storage of large amounts of data, and data communication technologies, document input, correction, editing,
Computer operation from layout to page set consistently,
2. Description of the Related Art An electronic editing system that can immediately output to a terminal block at a remote place by a high-speed communication network or satellite communication has been put to practical use. In particular, the demand for an electronic editing system is high in the newspaper printing field, which requires immediacy. Also, in the field where original manuscripts are currently stored in the form of a film, and based on this, printing plates are duplicated as necessary, the development of large-capacity recording media such as optical disks has resulted in the development of originals. It is considered that these recording media will be stored as digital data.

However, direct-type printing plates that create a printing plate directly from the output of a terminal plotter have hardly been put into practical use.
Even when the electronic editing system is running, the output is performed on a silver halide photographic film, and the printing plate is actually created by contact-exposing this to a PS plate. One of the reasons is that it is difficult to develop a direct type printing plate having a sensitivity high enough to produce a printing plate in a practical time by a light source of an output plotter (for example, a He-Ne laser, a semiconductor laser, etc.). Met.

An electrophotographic photoreceptor is considered as a photoreceptor having high photosensitivity capable of providing a direct printing plate.

Conventionally, printing plate material using electrophotography (printing plate)
For example, JP-B-47-47610, JP-B-48-4002
No., JP-B-48-18325, JP-B-51-15766, JP-B-51
Zinc oxide-resin dispersion offset printing plate materials described in, for example, JP-A-25761 and the like are known, which are made of a desensitizing solution (for example, , An acidic aqueous solution having a ferrocyanide salt or a ferricyanate salt).
The offset printing plate thus treated has a printing durability of 5
The number of sheets is about 1,000 to 10,000, which is not suitable for printing more than that, and if the composition is suitable for desensitization, there are disadvantages such as deterioration of electrostatic characteristics and deterioration of images. It also has the disadvantage of using harmful cyanide compounds as desensitizing solutions.

JP-B-37-17162, JP-B-38-7758, JP-B-46-3
No. 9405, JP-B No. 52-2437, etc., an organic photoconductor-resin printing plate material includes, for example, a light-sensitive material obtained by binding an oxazole or oxadiazole compound with a styrene-maleic anhydride copolymer. An electrophotographic photoreceptor having a conductive insulating layer provided on a grained aluminum plate is used. After forming a toner image on the photoreceptor by electrophotography, a non-image portion is dissolved and removed with an alkaline organic solvent. A printing plate is formed.

The present inventors have disclosed in JP-A-57-147656 an electrophotographic photosensitive printing plate material containing a hydrazone compound and barbituric acid or thiobarbituric acid. In addition, JP-A-59-147335, JP-A-59-152456
And JP-A-59-168462, JP-A-58-145495 and the like are known. However, the above-described dye-sensitized printing plate for electrophotographic plate-making does not provide sufficient sensitivity, and the development of a photoconductor having higher sensitivity has been desired. As means for realizing this, JP-A-55-161250, JP-A-56-146145,
Nos. 60-17751 and the like are known in which a phthalocyanine-based compound, an azo compound, a condensed polycyclic quinone compound, or the like is dispersed in a binding resin as a charge carrier-generating compound, but all have sufficient sensitivity or charge retention characteristics. I can't say it has been obtained.

[Problems to be solved by the invention]

Conventionally, triphenylmethane-based compounds in JP-B-45-555 and the like as charge transport materials, hydrazone compounds in JP-B-55-42,380, JP-A-54-150,128 and the like,
A number of triarylamine compounds have been proposed in Japanese Patent Publication No. 58-32,372. However, some photoreceptors manufactured using these charge transport materials exhibit relatively excellent electrophotographic performance, but their sensitivity is still insufficient, and their durability against light or electrical load is poor. Weak
A charge transport material that does not sufficiently satisfy practical requirements because it causes instability and deterioration in performance during repeated use, and has a more excellent charge transport function and stable performance for long-term use The development of was desired.

In addition, the above-mentioned electrophotographic printing plate precursor is not always satisfactory because the sensitivity for producing a direct printing plate is insufficient, and when the sensitivity is high, there are problems such as insufficient charge retention characteristics. I couldn't do it.

(Object of the present invention)

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member having an electrophotographic photosensitive layer containing a charge transporting substance having good transparency to light having a wavelength that generates charges.

Another object of the present invention is to provide an electrophotographic photoreceptor having an electrophotographic photosensitive layer that has a small dark decay of the potential, has high sensitivity, and has a small residual potential.

Another object of the present invention is to provide an electrophotographic photosensitive member having a stable electrophotographic photosensitive layer, which is stable against oxygen, light, and heat due to ozone generated by corona charging, and has little fluctuation in performance due to repeated use. is there.

Another object of the present invention is to provide an electrophotographic photoreceptor having an electrophotographic photosensitive layer containing a non-toxic charge transport material and which is safe to handle and dispose of.

Another object of the present invention is to provide an electrophotographic printing plate precursor having sufficient sensitivity to directly prepare a printing plate by using a laser or the like.

Another object of the present invention is to provide an electrophotographic printing plate precursor having excellent electrostatic characteristics.

Another object of the present invention is to provide an electrophotographic printing plate precursor having excellent printing characteristics.

[Means for solving the problem]

The problem with the electrophotographic photoreceptor is that an electrophotographic method is characterized in that a photosensitive layer containing at least one acetylene-based compound represented by the following general formula (I) is provided on a conductive support. The problem can be solved by a photoconductor.

Another problem with the electrophotographic printing plate precursor is that a conductive support has a photoconductive layer containing at least a charge generating substance, a charge transporting substance, and a binding resin, and the toner image is formed by electrophotography. Is formed, by removing the photoconductive layer in the non-image portion other than the toner image portion, the charge transport material is represented by the following general formula (I) in a printing plate precursor for electrophotographic plate making. The problem can be solved by a printing original plate for electrophotographic plate making, which is a compound.

General formula (I) In the formula, Ar ¹ and Ar ² represent an aromatic carbocyclic group or an aromatic heterocyclic group, and these groups may be further substituted with a substituent.

Ar ³ and Ar ⁴ represent a divalent aromatic carbocyclic group, and these groups may be further substituted by a substituent.

R represents an alkyl group, an aralkyl group, or an aryl group, and these groups may be further substituted with a substituent.

 The acetylene compound of the present invention will be described in detail.

When Ar ¹ and Ar ² are an unsubstituted aromatic carbocyclic group, specific examples include a phenyl group, a naphthyl group, an anthryl group, a pyrenine group, an acenaphthenyl group, a fluorenyl group and the like.

When Ar ¹ and Ar ² are an unsubstituted aromatic heterocyclic group, specific examples include a pyridinyl group, a quinolinyl group, an oxazolyl group,
And aromatic heterocyclic groups such as thiazolyl, oxadiazolyl, benzoxazolyl, benzoimidazolyl, benzothiazolyl, benzotriazolyl, dibenzofuranyl, carbazolyl, and xanthenyl.

Ar ³ and Ar ⁴ include, for example, phenylene, naphthalene,
Examples thereof include divalent groups derived from aromatic carbocyclic groups such as anthrylene, biphenylene, terphenylene and the like, and an arylene group, indene, fluorene, acenaphthene, azulene, perylene, fluorenone, anthrone, anthraquinone, benzanthrone and isocoumarin.

When Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are an aromatic carbocyclic group or an aromatic heterocyclic group having a substituent, specific examples of the substituent include an alkyl group having 1 to 18 carbon atoms (a methyl group, Ethyl group,
n-propyl group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxyl group, carboxyl group, alkoxy group having 1 to 18 carbon atoms (for example, methoxy group, ethoxy group) , A propoxy group, a butoxy group, etc.), an aryloxy group (for example, phenoxy group, o-tolyloxy group, m-tolyloxy group, p
-Tolyloxy group, 1-naphthyloxy group, etc.), dialkylamino group (for example, dimethylamino group, diethylamino group, dibutylamino group, etc.), diarylamino group,
(For example, diphenylamino group, phenyltolylamino group, etc.), N-alkyl-N-arylamino group, (for example, N-methyl-N-phenylamino group, N-ethyl-N-
Phenylamino group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), trialkylsilyl group (for example, trimethylsilyl group, t-butyldimethylsilyl group, etc.),
Examples include a halogenoalkyl group (eg, chloromethyl group, trifluoromethyl group, etc.) and an alkylthio group (eg, ethylthio group, ethylthio group, etc.). These substituents can be bonded to any number of carbon atoms of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ described above.

When R is an unsubstituted alkyl group, specific examples thereof include an alkyl group having 1 to 12 carbon atoms (for example, an ethyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, Hexyl group, cyclohexyl group, octyl group, nonyl group, dodecyl group, etc.).

When R is an alkyl group having a substituent, specific examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, a nitro group,
Hydroxyl group, carboxyl group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (for example, phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, 1-
A dialkylamino group (eg, dimethylamino group, diethylamino group, dibutylamino group, etc.), an aryl group (eg, phenyl group, naphthyl group, etc.),
Examples include a halogenoalkyl group (eg, chloromethyl group, trifluoromethyl group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, etc.). These substituents can be bonded to any number of carbon atoms of the aforementioned alkyl group.

When R is an unsubstituted aralkyl group, specific examples thereof include a benzyl group, a phenethyl group, a 1-naphthylmethyl group,
Examples thereof include a 2-naphthylmethyl group, a 1-anthrylmethyl group, and a benzhydryl group.

When R is an aralkyl group having a substituent, specific examples of the substituent include an alkyl group (a methyl group, an ethyl group, an n-
Propyl group) and the above-mentioned substituents of the alkyl group having a substituent. Any number can be substituted on any carbon atom of the aralkyl group of these substituents.

When R is an unsubstituted aryl group, specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a pyrenyl group, an acenaphthenyl group, and a fluorenyl group.

When R ¹ and R ² are a substituted aryl group, specific examples of the substituent include the same groups as the above-mentioned substituents of the substituted aralkyl group. It is.

Specific examples of the acetylene compound represented by the general formula (I) are shown below, but the present invention is not limited to the following specific examples.

As a representative method for producing the acetylene compound represented by the general formula (I), the following method can be mentioned. A compound represented by the following general formulas (II) and (III) and a bisaldehyde represented by the following general formula (IV) are reacted with an appropriate base (for example, hydrogen) in an organic solvent such as dimethylformamide, dimethylsulfoxide or tetrahydrofuran. Sodium chloride, sodium methoxide, potassium-t
-Butoxide or the like) to give an acetylene compound.

(Ar ¹ and Ar ² in the formula, Ar ¹ and Ar ² mentioned above in the general formula (I)
And Z represents a leaving group such as a tosyl group or a halogen atom. R 'represents a lower alkyl group such as a methyl group and an ethyl group. ) (Wherein, Ar ³ , Ar ⁴ and R represent Ar ³ , A in the aforementioned general formula (I)
It represents the same meaning as r ⁴ and R. The compounds of the general formulas (II) and (III) can be synthesized according to the synthesis method of Inokawa (Inogawa et al., The Chemical Society of Japan, 1974 , (6), 1093).

As the acetylene-based compound of the present invention, a photosensitive member according to the following embodiment formed on a conductive support can be used.

A single-layer photoreceptor in which a charge generating substance is dispersed in a charge transport medium comprising an acetylene compound and a binder.

A laminated photoreceptor comprising a charge generation layer containing a charge generation substance and a charge transport layer containing an acetylene compound.

1. A laminated photoreceptor comprising a charge generating layer containing a charge generating substance and an acetylene compound, and a charge transporting layer containing a charge transporting substance.

A single-layer photoreceptor containing a sensitizing dye and an acetylene compound at the same time.

In the case of the photoreceptor described above, the acetylene compound forms a charge transport medium together with a binder (or a binder and a plasticizer), while a charge generating substance such as an inorganic or organic pigment generates a charge. In this case, the charge transport medium mainly has the ability to receive and transport charge carriers generated by the charge generating substance. Here, it is a basic condition that the charge generation substance and the acetylene-based compound do not mutually have absorption wavelengths mainly in the visible region. This is because light must be transmitted to the surface of the charge generating material in order to generate charge carriers efficiently with the charge generating material. The acetylene-based compound of the present invention has a feature that it hardly absorbs in the visible region and generally functions as a charge transporting material when it is combined with a charge generating material that absorbs light in the visible region and generates charge carriers.

In the case of the photoreceptor, light transmitted through the charge transport layer reaches the charge generation layer, generation of charge carriers occurs in the charge generation layer, and the charge transport material receives injection of charge carriers and transports them. is there. In this case, the generation of the charge carriers is performed by the charge generating substance, and the transport of the charges is performed by the charge transport medium (mainly, the acetylene compound of the present invention works). is there.

In the case of the photoreceptor, the mechanism of charge generation and charge transport is the same as that of the photosensitive layer. However, in general, in a laminated type photoreceptor, the charge generating layer has a low moving speed of the charge carriers, so that the surface potential and the residual potential are liable to be easily increased during repeated use. By lowering the surface potential and increasing the residual potential upon repeated use by preventing the charge carrier from moving in the charge generation layer by increasing the moving speed of the charge carrier in the charge generation layer by blending an acetylene compound in the charge generation layer.

In the photoreceptor of (1), the acetylene-based compound acts as a photoconductive substance, and the generation and transport of charge carriers required for light attenuation are performed via the acetylene-based compound. However, since acetylene compounds hardly absorb light in the visible region, it is necessary to sensitize by adding a sensitizing dye having absorption in the visible region for the purpose of forming an image with visible light. is there.

The photoreceptor is prepared by dispersing fine particles of a charge generating substance in a solution in which an acetylene compound and a binder are dissolved, and coating and drying the fine particles on a conductive support. The photoreceptor is obtained by vacuum-depositing a charge-generating substance on a conductive support or dispersing fine particles of a charge-generating agent in an appropriate solvent in which a binder is dissolved as necessary. Apply the solution, dry it, and if necessary, finish the surface by a method such as buffing or adjust the film thickness. Is obtained. The photoreceptor is coated with a dispersion obtained by dispersing the fine particles of the charge generating agent and the acetylene-based compound on the conductive support in an appropriate solvent in which a binder is dissolved, if necessary, and drying, If necessary, the surface is finished by a method such as buffing or the film thickness is adjusted, and then a solution containing an acetylene compound and a binder is applied thereon and dried.
To prepare the photoreceptor, a sensitizing dye is dissolved in a solution in which an acetylene compound and a binder are dissolved, and the solution is coated on a conductive support and dried.

As the conductive support used in the electrophotographic photoreceptor of the present invention, aluminum, copper, a metal plate such as zinc,
A material obtained by depositing or dispersing a conductive material such as aluminum, indium oxide, tin oxide, or copper iodide on a plastic sheet or a plastic film of polyester or the like, or a paper treated with conductivity is used.

The coating can be performed by a usual means, for example, a doctor blade method, a weir bar method, an applicator method, a spray method, a dipping method, an extrusion method and the like.

The thickness of the photosensitive layer is 1 to 50 μm, preferably 5 to 20 μm for the photoreceptor. , The thickness of the charge generation layer is 5 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer is 3 to 50 μm, preferably 10 to 25 μm. 2 to 40 μm, preferably 5 to 20 μm
It is.

In the photoreceptor, the proportion of the acetylene compound in the photosensitive layer is 10 to 95% by weight, preferably 30 to 90% by weight, and the proportion of the charge generating substance is 50% by weight or less, preferably 20% by weight or less. The ratio of the acetylene compound in the charge transport layer in the photoreceptor is 10 to 95% by weight,
Preferably it is 30 to 90% by weight. The ratio of the charge generating material in the charge generating layer is 10 to 100% by weight, preferably 30 to 90% by weight in the case of the photoreceptor. In the charge generating layer of the photoreceptor, the charge generating substance is contained in an amount of 0.01 to 90% by weight, preferably 0.05 to 70% by weight, and the acetylene compound is contained in the amount of 0.1 to 7%.
In a photoreceptor used at 0% by weight, preferably 0.05 to 50% by weight, the ratio of the acetylene compound in the photosensitive layer is 10 to 95% by weight, preferably 25 to 80% by weight.

Further, a plasticizer can be used together with the binder in the photoreceptors (1) to (4).

As the binder used for the photoreceptor, it is preferable to use a film-forming high molecular polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. Examples of such a high-molecular polymer include the following, but are not limited thereto.

Polycarbonate, polyester, polyester carbonate, polysulfone, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer Coalescence, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol formaldehyde resin,
Styrene-alkyd resin, styrene-maleic anhydride copolymer, phenoxy resin, polyvinyl butyral resin, poly-N-vinyl carbazole.

These resin binders can be used alone or as a mixture of two or more.

As a plasticizer, biphenyl, biphenyl chloride, o-terphenyl, p-terphenyl, dibutyl phthalate,
Examples include dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, chlorinated paraffin, dilauryl thiodipropionate, and the like.

The sensitizing dye used for the photoreceptor of the present invention includes Brilliant Green, Victoria Blue B, Methyl Violet, Crystal Violet, Acid Violet 6B
Triallylmethane dyes such as Rhodanmin B, rhodamine 6G, rhodamine G extra, eosin S, erythrosin, rose bengal, fluorescein, etc .; hexaneazine dyes such as methylene blue; CIBasic.
Astrazone dyes such as Violet7 (CI48020), cyanine dyes, 2,6-diphenyl-4- (N, N-dimethylaminophenyl) thiapyrylium perchlorate, benzopyrylium salts (described in JP-B-48-25,658), etc. Pyrylium dyes.

Further, in order to improve the surface properties of the electrophotographic photoreceptor, silicone oil, fluorine-based surfactant and the like can be used.

As the charge generating substance, inorganic photoconductive materials such as selenium, selenium-tellurium, cadmium sulfide, and zinc oxide, and organic photoconductive materials shown in the following (1) to (9) can be used.

(1) U.S. Pat. Nos. 4,436,800 and 4,439,506;
No. 47-37543, No. 58-123,541, No. 58-192,042, No. 5
8-219,263, 59-78,356, 60-179,746, 6
Nos. 1-148,453, 61-238,063, JP-B-60-55941,
Monoazo, bisazo and trisazo pigments described in JP-A-60-45,664 and the like. (2) Phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine described in U.S. Pat. Nos. 3,397,086 and 4,666,802 (3) U.S. Pat. (4) Indigo and thioindigo derivatives described in US Pat. No. 2,237,680, etc. (5) Quinacridone pigments described in British Patent No. 2,237,679, (6) British Patent No. 2,237,678, JP No. 59-184,348,
Polycyclic quinone pigments described in JP-A-62-28,738 and the like (7) Bisbenzimidazole pigments described in JP-A-47-30331 and the like (8) Squarium described in U.S. Pat. Nos. 4,396,610 and 4,644,082 Salt-based pigments (9) Azurenium salt-based pigments described in JP-A Nos. 59-53,850 and 61-212,542, etc.
Species or two or more species may be used in combination.

 Of these charge generating substances, azo dyes are preferred.

In the present invention, the acetylene-type compound represented by the general formula (I) and one or more other charge transport materials can be used as a mixture as the charge transport material. Charge transport materials other than the acetylene-type compound of the present invention used in the charge transport layer are classified into two types: compounds that transport electrons and compounds that transport holes. Both can be used for the electrophotographic photoreceptor of the present invention.

Examples of the compound that transports electrons include compounds having an electron-withdrawing group, such as 2,4,7, -trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 9-
Dicyanomethylene-2,4,7-trintrofluorenone,
9-dicyanomethylene-2,4,5,7-tetranitrofluorenone, tetranitrocarbazole, chloranil, 2,3
-Dichloro-5,6-dicyanobenzoquinone, 2,4,7-trinitro-9,10-phenanthrenequinone, tetrachlorophthalic anhydride, teracyanoethylene, tetracyanoquinodimethane and the like.

Examples of the hole-transporting compound include compounds having an electron-donating group, for example, in the case of a polymer, (a) polyvinyl carbazole and its derivatives described in JP-B-34-10,966, and (b) JP-B-43-18,674. No. 43-19,192, polyvinyl pyrene, polyvinyl anthracene, poly-2
-Vinyl-4- (4'-dimethylaminophenyl) -5
Vinyl polymers such as -phenyloxazole and poly-3-vinyl-N-ethylcarbazole; and (c) polymers such as polyacenaphthylene, polyindene and copolymers of acenaphthylene and styrene described in JP-B-43-19,193. (D) Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-B-56-13,940, and (e) JP-A-56-90,883, and 56-16,550. Various kinds of triphenylmethane polymers described in Japanese Patent Publication Nos. JP-A-H11-176122 and low-molecular-weight polymers include (f) oxadiazole derivatives described in US Pat. No. 3,112,197, and (g) US Pat. No. 3,189,447. (H) imidazole derivatives described in Japanese Patent Publication No. 37-16,096, etc. Body, (i) U.S. Pat. No. 3,615,402, the 3,820,989 Patent, the 3,54
No. 2,544, JP-B-45-555, JP-B-51-10,983, JP-A-51
-93,224, 55-108,667, 55-156953, 56
Polyarylalkane derivatives described in JP-A-36,656, publications, etc .; (j) U.S. Pat. Nos. 3,180,729 and 4,278,746;
55-88,064, 55-88,065, 49-105,537, 5
5-51,086, 56-80,051, 56-88,141, 57
Nos. -45,545, 54-112,637, 55-74,546, pyrazoline derivatives and pyrazolone derivatives described in publications, etc .; (k) U.S. Pat. No. 3,615,404, Japanese Patent Publication No. 51-10,105,
Nos. 46-3,712 and 47-28,336, JP-A-54-83,435
And phenylenediamine derivatives described in JP-A-54-110,836, JP-A-54-119,925, publications, and the like. (1) U.S. Patent Nos. 3,567,450, 3,180,703, and 3,24
0,597, 3,658,520, 4,232,103, 4,175,961
No. 4,012,376, West German Patent (DAS) 1,110,518,
JP-B-49-35,702, JP-B-39-27,577, JP-A-55-144,
Nos. 250, 56-119,132 and 56-22,437, arylamine derivatives described in publications, etc .; (m) amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501; (n) U.S. Pat. No. 3,542,546 N, N-
A bicarbazyl derivative, (o) an oxazole derivative described in U.S. Pat. No. 3,257,203, (p) a styryl anthracene derivative described in JP-A-56-46234, and (q) a JP-A 54-110,837. (R) U.S. Pat. No. 3,717,462, JP-A-54-59,143 (corresponding to U.S. Pat. No. 4,150,987), and 55-52,063;
No. 55-52,064, No. 55-46,760, No. 55-85,495, No.
57-11,350, 57-148,749, 57-104,144, hydrazone derivatives described in publications, etc., (s) U.S. Patent Nos. 4,047,948, 4,047,949, 4,26
5,990, 4,273,846, 4,299,897, 4,306,008
(T) JP-A-58-190,953, JP-A-59-95,540, JP-A-59-9
Stilbene derivatives described in JP-A-7-148, JP-A-59-195,658, JP-A-62-36,674 and the like.

In the present invention, the compounds for transporting charge carriers are not limited to the compounds listed in (a) to (t), and all known charge carrier transport compounds can be used.

When producing the electrophotographic photoreceptor of the present invention, an additive such as a sensitizer may be added to the charge generation layer and the charge transport layer. Further, a charge transport compound may be added to the charge generation layer for use.

Examples of the sensitizer include chloranil, tetracyanoethylene, methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye, and thiapyrylium dye.

The electrophotographic photoreceptor of the invention may have an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary. As the material used for these layers, in addition to the polymer used for the resin binder,
Gelatin, casein, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, JP-A-59-8
There are vinylidene chloride-based polymer latex described in JP-A-4,247, styrene-butadiene-based polymer latex described in JP-A-59-114,544 or aluminum oxide, and the thickness of these layers is preferably 1 μm or less.

Although the electrophotographic photoreceptor of the present invention has been described in detail above, the electrophotographic photoreceptor of the present invention is generally characterized by high sensitivity and little change in electrophotographic characteristics when repeatedly used.

The electrophotographic photoreceptor of the present invention can be widely applied to fields such as a photoreceptor of a printer using a laser, a cathode ray tube, an LED or the like as a light source, in addition to an electrophotographic copying machine.

As the binder resin used in the electrophotographic printing plate precursor of the present invention, the toner image portion is not eluted, and the non-image portion (ie,
Any resin that dissolves or swells in a solvent that elutes the photoconductive layer can be used, but is preferably a resin that dissolves or swells in an alcohol and / or an alkaline aqueous solution. These resins include phenolic resins, styrene / maleic anhydride copolymers, vinyl acetate, crotonic acid copolymers, vinyl acetate / maleic anhydride copolymers, alcohol-soluble nylons, or acrylic acid, methacrylic acid, crotonic acid. Alternatively, there may be mentioned an acid group-containing monomer such as itaconic acid and a monomer such as methacrylic acid ester, acrylic acid ester or styrene and a copolymer of two or more elements, and any copolymer containing an acid group may be used. It is possible. More preferably, Japanese Patent Application No. Sho 63
The following copolymers described in JP-A-87024, Japanese Patent Application Nos. 63-1556387 and 63-158365 are preferably used.

That is, (a) at least one monomer component having a vinyl polymerizable monomer having an acidic functional group and having an acrylic acid ester or a methacrylic acid ester having an aromatic ring as at least one monomer component; A copolymer having the formula:

(B) A copolymer having a vinyl ester compound having an aromatic ring as at least one monomer component and having a vinyl polymerizable monomer having an acidic functional group as at least one monomer component.

(C) A copolymer having, as at least one monomer component, a compound obtained by half-esterifying maleic anhydride with an alcohol having an aromatic ring in the molecule, and having a styrene derivative as at least one monomer component. It is.

More preferably, at least one monomer having at least one vinyl polymerizable monomer having an acidic functional group and having an acrylic acid ester or methacrylic acid ester having an aromatic hydrocarbon ring as at least one monomer component. It is a copolymer having as a component. Since monomers are readily available, at least one vinyl-polymerizable monomer having benzyl acrylate or benzyl methacrylate as at least one monomer component and having an acidic functional group can be used. Copolymer having a monomer component such as methacrylic acid benzyl ester-methacrylic acid copolymer or methacrylic acid benzyl ester-
A copolymer such as an acrylic acid copolymer or a benzyl acrylate-acrylic acid copolymer is optimally used.

These resins can be used alone or in combination of two or more.

In the printing plate for electrophotographic plate making of the present invention, the ratio between the binding resin and the charge transporting substance can be used within a range in which the charge carrier transporting compound is compatible with the binding resin and does not precipitate. When the content of the charge transport material is small, the sensitivity is reduced. Therefore, the charge transport material is 0.05 to 1 part by weight of the binding resin.
3 parts by weight, preferably in the range of 0.1 to 1.5 parts by weight. On the other hand, if the content of the charge generating substance is too large, the charge retention characteristics deteriorate, and if the content is too small, the sensitivity decreases. Therefore, the content of the charge generating substance in the photoconductor is 1 part by weight of the binder resin. , 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight. On the other hand, if the photoconductive layer is too thin, there is no charge required for development. If the photoconductive layer is too thick, side etching occurs during etching, and a good image cannot be obtained. The thickness of the photoconductive layer is 0.1 to 30 μm, preferably 0.5 to 10 μm.

In the printing plate for electrophotographic plate making of the present invention, the charge generating substance is an inorganic photoconductive material such as selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the above-mentioned (1) to (1).
The organic photoconductive material shown in (9) can be used.

The photoconductive layer of the electrophotographic printing plate precursor of the present invention,
For the purpose of improving sensitivity, for example, trinitrofluorenone, chloranil, electron withdrawing compounds such as titracyanethylene, JP-A-58-65,439, JP-A-58-102,239,
Compounds described in JP-A-58-129,439 and JP-A-62-71,965 can be exemplified.

Various supports can be used as the conductive substrate of the printing plate precursor for electrophotographic plate making of the present invention. For example,
Plastic sheet with conductive surface or paper made especially solvent impervious and conductive, aluminum plate, zinc plate, or bimetal plate such as copper-aluminum plate, copper-stainless plate, chromium-copper plate, or chromium-copper- A conductive substrate having a hydrophilic surface such as a trimetal plate such as an aluminum plate, a chromium-lead-iron plate, and a chromium-copper-stainless plate is used, and the thickness thereof is preferably 0.1 to 3 mm, particularly 0.1 to 0.5 mm. Is preferred. Among these substrates, an aluminum plate is preferably used. The aluminum plate used in the present invention is a plate-like body such as pure aluminum containing aluminum as a main component or an aluminum alloy containing a trace amount of a different atom, and the composition thereof is not specified, and conventionally known and publicly available materials are appropriately used. Can be used.

This aluminum plate can be used after graining and anodizing by a conventionally known method. Prior to the graining treatment, a degreasing treatment with a surfactant or an alkaline aqueous solution is performed, if desired, to remove the rolling grease on the surface of the aluminum plate, and the graining treatment is performed. The graining method includes a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of chemically selectively dissolving the surface. As a method of mechanically roughening the surface,
Known methods called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method and the like can be used.
As an electrochemical surface roughening method, there is a method of performing countercurrent or direct current in a hydrochloric acid or nitric acid electrolyte. Also,
As disclosed in Japanese Patent Application Laid-Open No. 54-63,902, a method combining the two can also be used.

The roughened aluminum plate is subjected to an alkali etching treatment and a neutralization treatment as necessary.

The aluminum plate thus treated is anodized. As the electrolyte used for the anodizing treatment, sulfuric acid,
Phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used, and their electrolytes and their concentrations are appropriately determined depending on the type of the electrolyte. The anodizing treatment conditions vary depending on the electrolyte used, and thus cannot generally be specified. However, in general, the concentration of the electrolyte is 1 to 80% by weight, and the solution temperature is 5 to 70%.
° C, current density 5-60A / dm ² , voltage 1-100V, electrolysis time 10
It is preferable to be in the range of seconds to 50 minutes. The amount of anodic oxide film is
0.1 to 10 g / m ² is suitable, but more preferably 1 to 6 g / m ²
Range.

In the electrophotographic printing plate precursor of the present invention, an intermediate layer may be provided for the purpose of improving the adhesion between the conductive substrate and the photoconductive layer, the electrical properties of the photoconductive layer, the etching properties, the printing properties, and the like, if necessary. Can be.

As the intermediate layer, for example, casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-
Maleic anhydride resin, polyacrylic acid, monoethanolamine, diethanolamine, triethanolamine,
Tripropanolamine, triethanolamine and their hydrochlorides, oxalates, phosphates, aminoacetic acid, monoaminomonocarboxylic acids such as alanine, serine, threonine, oxyamino acids such as dihydroxyethylglycine,
Cysteine, amino acids containing sulfur such as cystine, aspartic acid, monoamino dicarboxylic acids such as glutamic acid,
Diaminomonocarboxylic acids such as lysine, amino acids having an aromatic nucleus such as p-hydroxyphenylglycine, phenylalanine and anthranilic acid, amino acids having a heterocyclic ring of tryptophan and prophosphoric acid, and aliphatic aminosulfones such as sulfamic acid and cyclohexyl sulfamic acid (Poly) such as acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminediacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and glycoletherdiaminetetraacetic acid
Aminopolyacetic acid and a part or all of the acid groups of these compounds may be sodium salts, potassium salts, ammonium salts and the like.

Further, in the printing plate precursor for electrophotographic plate making of the present invention, the photoconductive layer may be formed on the photoconductive layer, if necessary, in order to improve the electrical properties of the photoconductive layer, the image properties during toner development, the adhesion to the toner, and the like. An overcoat layer that can be removed during layer etching can be provided. The overcoat layer may be a mechanically matted one or a resin layer containing a matting agent. Examples of the matting agent include silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina, starch, resin particles (eg, polymethyl methacrylate, polystyrene, phenol resin, etc.) and US Pat. Nos. 2,710,245 and 2,992,101. Matting agents described in this document. These can be used in combination of two or more.

The resin used for the resin layer containing the matting agent is appropriately selected depending on the combination with the etchant used. Specifically, for example, gum arabic, glue, gelatin, casein, celluloses (eg, viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, etc.), starches (eg, soluble starch, modified starch, etc.) ), Polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl methyl ether, epoxy resin, phenol resin (particularly preferably a novolak phenol resin), polyamide, polyvinyl butyral, and the like. These can be used in combination of two or more.

The printing plate for electrophotographic plate making of the present invention can be obtained by applying a photoconductive layer on a conductive substrate according to a conventional method.
In producing the photoconductive layer, a method of including the components constituting the photoconductive layer in the same layer, or a method of separating and using a charge generating substance and a charge transporting substance in different layers is known. It can also be created by the method of.

The coating liquid is prepared by dissolving each component constituting the photoconductive layer in an appropriate solvent. When a component insoluble in a solvent such as a pigment is used, it is used after being dispersed to a particle size of 5 μm to 0.1 μm using a disperser such as a ball mill, a paint shaker, a dyno mill, and an attritor. The binder resin and other additives used in the photoconductive layer can be added during or after the dispersion of the pigment or the like. Spin coating, blade coating, knife coating, reverse roll coating,
An electrophotographic printing plate can be obtained by coating and drying on a substrate by a known method such as dip coating, rod bar coating and spray coating. Examples of the solvent for preparing the coating liquid include halobanated hydrocarbons such as dichloromethane, dichloroethane, and chloroform; alcohols such as methanol and ethanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethylene glycol monomethyl ether; and 2-methoxyethyl acetate. And ethers such as tetrahydrofuran and dioxane, and esters such as ethyl acetate and butyl acetate.

In the photoconductive layer of the present invention, in addition to the photoconductive compound and the binder resin, for the flexibility of the photoconductive layer, improvement of the coated surface, etc., if necessary, a plasticizer, a surfactant, a matting agent and other various Additives can be added. These additives can be contained within a range that does not deteriorate the electrostatic properties and etching properties of the photoconductive layer.

The printing plate for electrophotographic plate making of the present invention can be prepared by a generally known process. That is, it is charged substantially uniformly in a dark place, and forms an electrostatic latent image by image exposure. Examples of the exposure method include scanning exposure using a semiconductor laser, a He-Ne laser, or the like, reflection image exposure using a xenon lamp, tungsten lamp, fluorescent lamp, or the like as a light source, and contact exposure through a transparent positive film. Next, the electrostatic latent image is developed with toner. As the developing method, various conventionally known methods such as cascade development, magnetic brush development, powder cloud development, and liquid development can be used. Among them, liquid development is capable of forming a fine image, and is suitable for preparing a printing plate. The formed toner image can be fixed by a known fixing method, for example, heat fixing, pressure fixing, solvent fixing and the like. The printing plate can be prepared by using the toner image thus formed as a resist and removing the electrophotographic photosensitive layer in the non-image area with an etchant.

As an etchant for removing the photoconductive insulating layer of the toner non-image portion after forming the toner image, any solvent can be used as long as it can remove the photoconductive insulating layer, and there is no particular limitation. However, preferably, an alkaline solvent is used. Here, the alkaline solvent is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic solvent.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium phosphate, ammonia,
And any organic and inorganic alkaline compounds such as amino alcohols such as monoethanolamine, diethanolamine and triethanolamine. As a solvent for the etching solution,
Water or many organic solvents can be used,
An etchant mainly composed of water is preferably used in view of odor and pollution.

Various organic solvents can be added to the etching solution mainly composed of water, if necessary. Preferred organic solvents include methanol, ethanol, propanol,
Lower alcohols and aromatic alcohols such as butanol, benzyl alcohol and phenethyl alcohol, and ethylene alcohol, diethylene glycol, triethylene glycol, polyethylene glycol, cellsolves, and amino alcohols such as monoethanolamine, diethanolamine, and triethanolamine. Can be done.

As the etching solution, a solution containing a surfactant, an antifoaming agent, and other various additives as necessary is used.

The toner for forming an image portion in the printing plate precursor for electrophotographic plate making of the present invention is not particularly limited as long as it has a resist property to the etching solution. It is preferable to contain a resin component having a property.

Examples of the resin component include methacrylic acid, acrylic acid and acrylic resins using these esters, vinyl acetate resins, copolymer resins such as vinyl acetate and ethylene or vinyl chloride, vinyl chloride resins, vinylidene chloride resins, and polyvinyl butyral. Vinyl acetal resin, polystyrene, copolymer resin such as styrene and butadiene, methacrylate, polyethylene, polypropylene and chlorinated product thereof, polyester resin (for example, polyethylene terephthalate, polyethylene isophthalate, polycarbonate of bisphenol A, etc.), phenol resin, Xylene resins, alkyd resins, vinyl-modified alkyd resins, gelatin, cellulose ester derivatives such as carboxymethyl cellulose, waxes, polyolefins, waxes, etc.

〔Example〕

Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples. In the examples, “parts” means “parts by weight”.

Example 1 Selenium was vacuum-deposited to a thickness of 0.4 μm on a grained aluminum plate having a thickness of about 300 μm to form a charge generation layer. On this, 10 parts of an acetylene-based compound represented by the above-mentioned specific example (A-1) of a compound and a polycarbonate of bisphenol A (trade name Panlite K, manufactured by Teijin Limited)
-1300) A solution of 10 parts dissolved in 130 parts of dichloromethane was applied using an applicator, and then a dried charge transport layer having a thickness of about 14 μm was formed.

This photoreceptor was charged for 5 seconds with a corona discharge of -5 KV using an electrostatic copying paper tester (SP-428, manufactured by Kawaguchi Electric Works) and surface potential when left in a dark place for 10 seconds. V _O, then light is irradiated such that its surface by a tungsten lamp of color temperature 2854K is 2 lux, the sensitivity (half decay exposure, E50) were measured. The result is V
_O = −810 V and E50 = 1.5 lux · sec.

Examples 2 to 6 A photoreceptor having a two-layer structure was prepared in the same manner as in Example 1 except that the acetylene-based compound (A-1) was replaced with the acetylene-based compound shown in Table 1 in Example 1. And
In the same manner as in Example 1, the surface potential V _O due to negative charging and the half-life exposure amount E50 were measured. Table 1 shows the results.

Example 7 5 parts of X-type metal-free phthalocyanine was added to 660 parts of dichloromethane, and the mixture was ultrasonically dispersed. Then, 40 parts of a polycarbonate of bisphenol A (Panlite K-1300) and a specific example of a compound (A- 40 parts of the acetylene compound represented by 3) was added and dissolved to prepare a coating solution. Using a wire round rod, apply this coating solution to a conductive support (on a 100 μm polyethylene terephthalate support,
With a deposited film of indium oxide. Surface resistance 10 ³ Ω
₀ ), and dried to obtain a photoreceptor having a thickness of about 10 μm.

The photoreceptor was charged for 3 seconds by +5 KV corona discharge, and the surface potential V _O when left in a dark place for 10 seconds, and then the half-life exposure E50 when exposed at an illuminance of 2 lux were measured. As a result, V _O = + 550 V and E50 = 2.1 lux · sec.

Example 8 2 parts of a trisazo pigment represented by the following structural formula (V) and a polyester resin (manufactured by Toyobo Co., Ltd., trade name: Byron 20)
0) 2 parts were added to 7 parts of tetrahydrofuran and dispersed in a ball mill for 12 hours, and then this dispersion was deposited on a conductive support (75 μm polyethylene terephthalate support with an aluminum vapor-deposited film) using a wire round rod. Product name Metal Me 75TS, manufactured by Toray Industries, Inc.)
After drying, a charge generation layer having a thickness of about 0.5 μm was obtained.

Next, 3.6 parts of the acetylene compound represented by the specific example (A-1) of the compound was
A solution prepared by dissolving 4 parts of a polycarbonate (manufactured by Teijin Limited, trade name: Panlite K-1300) in a solution composed of 13.3 parts of dichloromethane and 26.6 parts of dichloroethane is applied using an applicator, and a charge transport layer having a thickness of 17 μm is applied. Was formed to prepare an electrophotographic photosensitive member having a photosensitive layer composed of two layers.

Further, as comparative examples, comparative examples 1 and 2 were prepared using the following structural formulas (B-1) and (B-2) as charge transporting agents in place of the acetylene compound (A-1).

These photoreceptors were evaluated for electrophotographic characteristics (measured by a static method) using an electrostatic copying paper test apparatus (SP-428, manufactured by Kawaguchi Electric Works, Ltd.) as follows. First, the initial surface potential V _S when the photoreceptor was charged by corona discharge of −6 KV, and the surface potential V _O when left in a dark place for 30 seconds were measured. Then the light from a tungsten lamp was exposed so as to become the illuminance 3lux the photoconductor surface, the surface potential is required to attenuate to a half of the initial surface potential V _O exposure E50
The surface potential (residual potential V _R ) after 30 seconds of exposure was measured. The same measurement was repeated 3000 times. The results are shown in Table 2.

In addition, these photoreceptors are used in copiers (Sharp Corporation, SF
When the image was evaluated with the photoconductor of Example 1, a sharp and uniform image was obtained. On the other hand, the photoconductors of Comparative Examples 1 and 2 had white spots on black solid portions. White solid fog and black spots were noticeable.

As in Example 9-20 charges other using acetylene compounds shown in Table 3 as transport materials in the same manner as in Example 8 to create the electrophotographic photosensitive member of the two-layer structure Example 1 E50, V _S , it was measured V _O, V _R. The results are shown in Table 3.

Example 21 3 parts of an acetylene compound represented by the specific example (A-4) of the compound of the present invention and a polyester resin (Toyobo Co., Ltd.)
5 parts of disazo pigment represented by the following structural formula (VI) was added to a solution prepared by dissolving 5 parts of Byron 200) in 44 parts of tetrahydrofuran, and dispersed by a ball mill for 12 hours. A charge generating layer having a thickness of about 0.5 μm is coated on a conductive support (having a deposited film of aluminum on a 75 μm polyethylene terephthalate support. Metal Me 75TS, manufactured by Toray Industries, Inc.) and dried. I got

Next, 3.6 parts of a hydrazone compound represented by the following structural formula (VII) was formed on this charge generating layer by a polycarbonate of bisphenol A (trade name: Panlite K-130, manufactured by Teijin Limited).
0) 4 parts, 13.3 parts of dichloromethane and 26 parts of dichloroethane.
A solution dissolved in a solution consisting of 6 parts was applied using an applicator to form a charge transport layer having a thickness of 17 μm, thereby preparing an electrophotographic photosensitive member having a photosensitive layer consisting of two layers.

Further, as a comparative example, a photoconductor comparative example 3 in which the acetylene compound (A-4) was not contained in the charge generation layer was prepared.

E50, V _S , V _O , and V _R were applied to these photosensitive members in the same manner as in Example 1.
Was measured. The results are shown in Table 4.

From the results shown in Table 3, it was found that the photoreceptor of Example 21 in which the acetylene compound was added to the charge generation layer was superior to the photoreceptor of Comparative Example 3 in the sensitivity and the stability of the potential upon repeated use. .

Example 22 A copolymer of 5 parts of the trisazo pigment (V), 40 parts of an acetylene compound (A-6), benzyl methacrylate and methacrylic acid ([η] at 30 ° C. methyl ethyl ketone = 0.12, methacrylic acid) used in Example 8 Content 32.9%) 100
And 660 parts of dichloromethane, and add 12 with a ball mill.
Time dispersed. This dispersion was applied on a grained aluminum plate having a thickness of 0.25 mm and dried to prepare an electrophotographic printing plate material having an electrophotographic photosensitive layer having a thickness of 6 μm.

The surface potential of the photosensitive layer was charged to +500 V by corona discharge (+6 KV) in a dark place.
When exposed to tungsten light of 2854K at an illuminance of 2.0 lux on the test surface, the half-life exposure amount (E50) was 2.4 lux · sec.

Next, in this test, after the surface potential was charged to +500 V in a dark place, the image was exposed in close contact with a transparent original of a positive image. This is immersed in a liquid developer composed of IsoperH (a petroleum-based solvent manufactured by Esso Standard Co., Ltd.) 1, 5 g of polymethyl methacrylate (toner) dispersed in fine particles, and 0.01 g of soybean oil lecithin to give a clear positive toner. Images were obtained.

Heating was further performed at 100 ° C. for 30 seconds to fix the toner image.
The printing plate material was dissolved in 70 g of sodium metasilicate hydrate in 140 ml of glycerin, 550 ml of ethylene glycol and 150 ml of ethanol, immersed in an etching solution for 1 minute, and washed while gently brushing with a stream of water to remove toner. The printing layer was obtained by removing the portion of the photosensitive layer that was not present.

The printing plate produced in this way is Hamadastar 600CD
When printing was carried out using an offset printing machine, 50,000 sheets of very clear prints without background contamination could be printed.

Example 23 8 parts of an acetylenic compound (A-28), 10 parts of a polycarbonate of bisphenol A (Vanlite K-1300),
0.12 parts of an astrazone dye having the following structural formula was added to and dissolved in 110 parts of dichloromethane to prepare a coating solution.

The coating solution was applied to a conductive transparent support (a 100 μm polyethylene terephthalate support having an indium oxide deposited film on a conductive round support using a wire round rod. Surface resistance 10).
³ Ω ₀ ) and dried to obtain a photoreceptor having a thickness of about 10 μm.

After positively charging this photoreceptor by corona discharge of +5 KV, E50 was measured in the same manner as in Example 1, and E50 =
It was 9.6lux · sec.

(Effects of the Invention) By using the acetylene-based compound of the present invention as a charge transporting substance, an electrophotographic photosensitive member having high sensitivity, excellent repeatability, and excellent image uniformity can be realized. Further, by using the acetylene-based compound of the present invention as a charge transporting substance, a printing original plate for electrophotographic plate making having high sensitivity and excellent printing characteristics can be realized.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-60-73543 (JP, A) JP-A-3-75659 (JP, A) JP-A-56-80057 (JP, A) JP-A-59-0057 168454 (JP, A)

Claims (2)

(57) [Claims] 1. An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing at least one acetylene compound represented by the following general formula (I). In the formula, Ar ¹ and Ar ² represent an aromatic carbocyclic group or an aromatic heterocyclic group. Ar ³ and Ar ⁴ represent a divalent aromatic carbocyclic group. R represents an alkyl group, an aralkyl group, or an aryl group. 2. A photoconductive layer containing at least a charge generating substance, a charge transporting substance, and a binder resin on a conductive support, and after forming a toner image by electrophotography, a portion other than the toner image portion is formed. Wherein the charge transport compound is a compound represented by the following general formula (I) in the electrophotographic printing plate precursor for forming a printing plate by removing the photoconductive layer in the non-image portion. A printing original plate for photolithography. In the formula, Ar ¹ and Ar ² represent an aromatic carbocyclic group or an aromatic heterocyclic group. Ar ³ and Ar ⁴ represent a divalent aromatic carbocyclic group. R represents an alkyl group, an aralkyl group, or an aryl group.