JPS58219263A - Disazo compound, photoconductive composition containing the same, and photosensitive material for electro- photography - Google Patents

Abstract

NEW MATERIAL:The compound of formula I {A is group of formula II, etc.; B is group of formula III or formula IV [X is atomic group forming aromatic ring such as naphthalene ring, etc. or heterocyclic group such as indole ring, etc. together with a benzene ring bonded with OH and the group of Y; Y is group of formula V, etc.; R<1> is alkyl or phenyl; R<4> is H, alkyl or phenyl; R<5> is alkyl, aromatic group, heterocyclic group, etc.]}. EXAMPLE:The compound of formula VI. USE:A photosensitive material for electrophotography. It has high sensitivity and durability. PROCESS:The objective compound can be prepared, e.g. by diazotizing bis(4- aminostyryl)naphthalene, separating the resultant tetrazonium salt, and coupling the salt with a coupler such as naphthol AS, etc. in an organic solvent such as DMF in the presence of an alkali.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel disazo compound, a photoconductive composition containing this disazo compound, and an electrophotographic photoreceptor having an electrophotographic photosensitive layer containing this disazo compound.

The photoconductive process of an electrophotographic photoreceptor is (1) the process of generating electric charge by exposure to light; (2)
The process of transporting charges, consists of .

A selenium photosensitive plate is an example of performing (1) and (2) using the same material. On the other hand, the combination of amorphous selenium and poly-N-vinylcarbazole is well known as an example of performing (11 and (2) using different materials). The selection range of materials used in photoreceptors has been expanded, and the sensitivity of electrophotographic photoreceptors has increased accordingly.
It has the advantage that electrophotographic properties such as acceptance potential are improved, and materials convenient for preparing electrophotographic photoreceptor coatings can be selected from a wide range.

Conventionally, selenium,
There are inorganic substances such as cadmium sulfide and zinc oxide.

Electrophotography has already been published by Carlson in the United States - No. 2297
As disclosed in No. 691, a photoconductive material is used consisting of a support coated with a dark insulating substance whose electrical resistance changes depending on the amount of radiation received during image exposure. The photoconductive material is generally first given a uniform surface charge in the dark after dark adaptation for a suitable period of time. This material is then imagewise exposed to radiation, a pattern of radiation that has the effect of reducing the surface charge depending on the relative energy contained in the various parts of the e-turn. The surface charge or electrostatic latent image left on the surface of the photoconductive material layer (electrophotographic photosensitive layer) in this way is then treated with a suitable electrometric indicator material.
That is, it is brought into contact with toner and becomes a visible image.

The toner is contained in an insulating liquid or in a dry carrier, and in either case, it can be deposited on the surface of the electrophotographic photosensitive layer depending on the charge pattern. The deposited display material can be fixed by known means such as heat, pressure, and solvent vapor. The electrostatic latent image can also be transferred to a second support (eg, paper, film, etc.). It is likewise possible to transfer the electrostatic latent image to a second support and develop it there. Electrophotography is one of the image forming methods in which images are formed in this manner.

The basic characteristics required of an electrophotographic photoreceptor in such an electrophotographic method are (1) ability to be charged to an appropriate potential in a dark place, (2) less dissipation of charge in a dark place, ( 3) Examples include scales that quickly dissipate charge when irradiated with light.

It is true that the conventionally used inorganic materials have many advantages, but also have various disadvantages. For example, selenium, which is currently widely used, fully satisfies the conditions (11 to (3)) above, but the manufacturing conditions are difficult, the manufacturing cost is high, it is not flexible, and it cannot be processed into a belt shape. They also have disadvantages, such as being difficult and sensitive to heat and mechanical shock, requiring careful handling.Cadmium sulfide and zinc oxide are used as electrophotographic photoreceptors by dispersing them in a resin as a binder. There are, but
It cannot be used repeatedly as it is because of mechanical defects such as smoothness, hardness, tensile strength, and resistance to mechanical abrasion.

In recent years, electrophotographic photoreceptors using various inorganic materials have been proposed in order to eliminate the drawbacks of these inorganic materials, and some of them have been put into practical use. For example, poly-N-vinylcarbazole and 2.4.7-)linitrofluorene-9-
An electrophotographic photoreceptor (U.S. Pat. No. 3,484,
No. 237), poly-N-vinylcarbazole sensitized with pyrylium salt dyes (Japanese Patent Publication No. 25658, 1983), and electrophotographic photoreceptors whose main components are organic pigments (Japanese Patent Publication No. 1983).
6-1194, JP 53-133445, JP 56-116039, JP 47-37543),
This is an electrophotographic photoreceptor (JP-A-47-1 [1755]) whose main components are a eutectic complex consisting of a dye and a resin.

Although these organic electrophotographic photoreceptors have improved the mechanical properties and flexibility of the inorganic electrophotographic photoreceptors to some extent, they generally have low photosensitivity and are not suitable for repeated use, so they do not meet the requirements of electrophotographic photoreceptors. was not satisfactory.

As a result of intensive research to improve the drawbacks of the conventional electrophotographic photoreceptors, the present inventor, Nagisa et al., found that the electrophotographic photoreceptor containing the novel disazo compound of the present invention has a high sensitivity that can be put to practical use.・The present invention was achieved by discovering that the material is durable.・1,・
i The present invention relates to a novel disazo compound (disazo pigment) represented by the following general formula [1], a photoconductive composition containing the same, and an electrophotographic photoreceptor having an electrophotographic photosensitive layer containing the same. It is something.

The present invention provides (1) a disazo compound represented by the following general formula [1], in which A is any of the following groups.

B represents or is condensed with the Banze/ring in the above formula in which a hydroxy group and Y are bonded to form an aromatic ring such as a naphthalene ring or anthracene ring, or an indole ring, a carbazole ring, a dibenzofuran ring, etc. represents an atomic group necessary to form a heterocycle (both rings may be substituted or unsubstituted), R1 represents an alkyl group, a phenyl group, or a substituted product thereof, and R2 represents a hydrogen atom, lower alkyl group, carbamoyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, or substituted or unsubstituted amino group, R3 and R5 are alkyl group, phenyl group, naphthyl group,
Aromatic ring groups such as anthracene ring groups, diazofuranyl groups, carbazolyl groups, benzocarbazolyl groups, indo-
(2) In the general formula [1] above, A photoconductive composition characterized by containing a disazo compound represented by the above formula, and (3) an electrophotographic composition characterized by having an electrophotographic photosensitive layer containing a disazo compound represented by the above general formula [1]. Regarding photoreceptors.

The disazo compound represented by the general formula [1] will be explained in more detail.

Or a human 90 xyl group and Y are fused with an inzene ring to form an aromatic ring such as a naphthalene ring, anthracene ring, or a heterocyclic ring such as an indole ring, a carbazole ring, a benzocarbazole ring, or a divanzofuran ring. It is a group that can be formed.

When X is an aromatic ring or a heterocyclic ring having a substituent, the substituent is a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a lower alkyl group, preferably a carbon number of 1 to 8
lower alkyl groups (for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, etc.), and the number of substituents is 1 or 2, and when there are 2 substituents, may be the same or different.

R1 is an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, or a phenyl group.

1.

When R is an unsubstituted alkyl group, specific examples include methyl group, ethyl group, propyl group, butyl group,
hexyl group, isopropyl group, inmethyl group, isoamyl group, isohexyl group 5, l-pentyl group, tert
-Butyl group, etc. can be mentioned.

When R1 is a substituted alkyl group, the substituent includes a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a cyano group, an amino group, an alkylamino group having 1 to 12 carbon atoms, and an alkylamino group having 1 to 12 carbon atoms.
Examples thereof include a dialkylamino group having two alkyl groups of 12, a norogen atom, and an aryl group having 6 to 15 carbon atoms. Specific examples include dimethyl group, 2-human 80xyethyl group, 3-hybiloxypropyl group, 2-human 90xypropyl group, etc.), alkoxyalkyl group (such as methoxymethyl group, 2-methoxyethyl group, ro-methoxy zorobyl group, ethoxymethyl group, 2-ethoxyethyl group, etc.), cyanoalkyl group (e.g., cyanmethyl group, 2-cyanethyl group, etc.), aminoalkyl group (e.g., aminomethyl group, 2-aminoethyl group, 6-aminoethyl group, etc.),
(Alkylamino)alkyl group (e.g. methylamine) methyl group, 2-(methylamine)ethyl group, (ethylamine)methyl group, (dialkylamino)alkyl group (
(dimethylamino)methyl group, 2-(dimethylamino)ethyl group, etc.), halogenoalkyl group (e.g., fluoromethyl group, chloromethyl group, bromomethyl group, etc.)
, aralkyl groups (eg, benzyl group, phenethyl group, etc.).

When R is a substituted phenyl group, the substituent includes a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a cyan group, an amine group, an alkylamino group having 1 to 12 carbon atoms, and an alkylamino group having 1 to 12 carbon atoms.
Examples include a dialkylamino group having two alkyl groups of 12, a halogen atom, an alkyl group having 1 to 2 carbon atoms, and a nitro group. Examples include hydroxyphenyl group, alkoxyphenyl group (e.g., methoxyphenyl group, ethoxyphenyl group, etc.), cyanophenyl group, aminophenyl group, (alkylamino)phenyl group (for example, (methylamino)phenyl group, (ethylamino)phenyl group, etc.)
, (dialkylamino)phenyl group (e.g., (dimethylamino)phenyl group, etc.), halogenophenyl group (e.g., fluorophenyl group, chlorophenyl group, bromophenyl group, etc.), alkylphenyl group (e.g., tolyl group, ethylphenyl group) , cumenyl group, xylyl group, medi f
14, etc.), nitrophenyl groups, and their substituents (
They may be the same or different. ) (the position of the substituent or the mutual positional relationship of the plurality of substituents is arbitrary).

R is a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms,
Carbamoyl group, carboxyl group, alkoxycarbonyl group having an alkoxy group having 1 to 12 carbon atoms, 6 carbon atoms
An aryloxycarbonyl group having ~20 aryloxy groups and a substituted or unsubstituted amino group are preferred.

When R2 is a substituted amine group, specific examples include a methylamino group, ethylamino group, propylamine group, phenylamino group, tolylamino group, benzylamino group, phenethylamino group, dimethylamino group, diethylamino group,
Examples include diphenylamino group.

2.

When R is a lower alkyl group, specific examples include methyl group, ethyl group, propyl group, methyl group, isopropyl group,
Examples include isobutyl group.

When 2 or R is an alkoxycarbonyl group, specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, impropoxycarbonyl group, benzyloxycarbonyl group, and the like.

2.

When R is an aryloxycarbonyl group, specific examples thereof include a phenoxycarbonyl group and a doloxycarbonyl group.

R and R are alkyl groups having 1 to 20 carbon atoms; aromatic ring groups such as phenyl and naphthyl groups; oxygen atoms, nitrogen atoms, and sulfur atoms such as dibenzofuranyl groups, carbazolyl groups, and benzocarbazolyl groups; A heteroaromatic ring group or a substituted product thereof is preferred.

In the case of R or R or a substituted or unsubstituted alkyl group,
Examples thereof include the same groups as the substituted or unsubstituted alkyl group for H described above.

When R or R is a substituted aromatic group such as a substituted phenyl group, a substituted naphthyl group, a substituted heteroaromatic group containing a heteroatom such as a substituted dibenzo7ranyl group or a substituted carbazolyl group,
Examples of substituents/groups include hydroxyl group, cyan group, nitro group, halogen atom (e.g., fluorine atom, chlorine atom,
bromine atom, etc.), an alkyl group having 1 to 12 carbon atoms (e.g.
(methyl group, ethyl group, propyl group, isopropyl group, etc.)
, an alkoxy group having 1 to 12 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, isopropoxy group, isobutoxy group, isoamyloxy group, tert-butoxy group, neopentyloxy group, etc.) , amine group, alkylamino group having 1 to 12 carbon atoms (e.g. methylamino group, ethylamino group, propylamine group, etc.), dialkylamino group having 1 to 12 carbon atoms (e.g. dimethylamino group, diethylamino group, N −
methyl-N-ethylamino group, etc.), an arylamino group having 6 to 12 carbon atoms (e.g., phenylamino group, tolylamino group, etc.), a diarylamino group having two aryl groups having 6 to 15 carbon atoms (e.g., diphenylamine base, etc.)
, carboxyl group, alkali metal carboxylad group (examples of alkali metals (cations), Na insects ■, Li■, etc.)
, alkali metal sulfonate group (examples of alkali metal (cation), Na"q K■, L1■, etc.), arylcarbonyl group (for example, acetyl group, propionyl group, benzylcarbonyl group v?,), carbon number -6 ~12 aryl group) f'J arylcarbonyl group (e.g., benzoyl group, toluoy A4, furoyl group, etc.), carbon number 1~
12 alkylthio groups (e.g., methylthio group, ethylthio group, etc.), or arylthio groups having 1 to 12 carbon atoms (
For example, phenylthio group, tolylthio group, etc.), the number of substituents is 1 to 6, and when multiple substituents are bonded, they may be the same or different from each other. Any combination may be used, and the bonding positions of the substituents are arbitrary.

R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
A phenyl group or a substituted product thereof.

4.

When R is a substituted or unsubstituted argyl group or a phenyl group, the same groups as the above-mentioned examples of substituted or unsubstituted alkyl groups and phenyl groups for R and H can be mentioned.

A derived from a coupler provides a photoconductive composition or an electrophotographic photosensitive layer with high photosensitivity, and the raw material compound can be easily obtained, making it possible to produce a disazo compound at low cost. From one point of view:, x;.

In addition, as X, a benzene ring and a carmesol ring, and specific examples of the compounds of the present invention are given below.

Since the part is common to the following compounds (2A) - (66A), it will be abbreviated as Zl hereinafter.

NH-@ (1A) H3 0H H3 H (53A) 5o3H,803H CH3CH3 CI CI 803H5O3H CH3CH3 CI C1 (520) RCA' NO□ N02 (51D) (52D) 803H803H (52E) So3H, 5o3H CH2O) 13 C Aya C7 Since the part is common to the following compound (2F) -<66F>, it will be abbreviated as Z6 hereinafter.

No2 N02 (51F) (52F) 81J 3 M Since the part 81J 3 M is common to the following compound (2G) - (66C,), it will be abbreviated as Z7 hereinafter.

(1G) No2N02 (51G) (5 lights) So3H803H CH3CH3 is the same lf in compound (2H)-(66H), so it will be abbreviated as z8 below.

(1H) Br Br (31H) (34H) -489- (51H) (52H) SO3H803H CH3CH3 Cl C1 The novel disazo compound of the present invention can be produced by a known method. That is, bis(4-aminostyryl)naphthalene is diazotized and isolated as a tetrazonium salt, and then diazotized and isolated as a tetrazonium salt.
- It can be easily produced by carrying out a coupling reaction with a compound corresponding to each of the above-mentioned pigments (for example, a naphthol As-based coupler) in dimethylformamide in the presence of an alkali.

The disazo compound of the present invention can be used as a disazo pigment.

For example, the disazo compound (1G) can be produced according to Synthesis Example 1.

Examples of synthesis of the disazo compound of the present invention will be specifically explained below.

Synthesis Example 1 1. s-his(4-aminostyryl)naphthalene 15.
8 g was added to dilute hydrochloric acid prepared from 4QrIL of Sta acid and 4Urnl of water, and the mixture was thoroughly stirred on a 60C water bath for about 60 minutes. This mixture was then cooled to OC and a solution of 631 g of sodium nitrite dissolved in 20 ml of water was added to it.
The mixture was added dropwise at C over a period of about 60 minutes.

Thereafter, the mixture was stirred at the same temperature for 1 hour, the resulting tetrazonium chloride salt was separated from P, the tetrazonium salt was dissolved in water, and the solution and the t1 liquid were combined. 40 ml of 42% borofluoric acid was added to the combined solution, and the precipitated crystals were collected for t''N.

After washing the crystals with a small amount of cold water, they were dried and 21 g of orange-red crystals of tetrazonium fluoroborate (yield: 86%) were obtained.
) was obtained.

Next, the thus obtained tetrazonium i2. og and 2-hydroxy-ro-naphthoic acid anilide i, s s , v as a coupler was dissolved in 120 mz of N,N-dimethylformamide 9 and a solution consisting of 4 sodium acetate and 20 ml of water was added to it at a temperature of OC. The mixture was added dropwise over 20 minutes, and then stirred at ¥300,000 for about 2 hours. After that, 1jj of the generated precipitate was collected, washed with water in step 11, and then washed with water in step 2001.
of N,N-dimethylformamide with stirring. Next, it was washed with ethanol and dried to obtain 2.89 g (yield: 89%) of a disazo pigment of compound (1). Minj'J
'f 11J: 30 U t? More elemental analysis Ce
As oH4z04N6 - Subtraction value C, 79, 1% H, 4, 65% N, 9.2
2% actual value c, 79o%H, 4,88%N, 9ro 14
IR absorption is Kutor (KBY tablet) Amide l575crrL-' Absorption thickest wavelength 540 nm (in dichloromethane solution) Synthesis Examples 2 to 22 A disazo compound was prepared in the same manner as in Synthesis Example 1, except that the compound listed in Table 1 was used as a coupler. (2G), (6C),
(4C), (5G), (11G), (13G), (15
0), (25G), (26G), (48G), (1G)
, (2G), (6a), (4G), (5G), (IIG
), (13G), (15G), (25G), (26G)
, (48G) were synthesized.

Decomposition temperature, elemental analysis value, I of each disazo compound
R absorption spectrum 5 Visible absorption spectra are shown in Table 1.

The infrared absorption spectra (KBr method) of disazo compounds (2G) and (11G) are shown in FIG.

Other disazo compounds can also be synthesized according to the above synthesis example, except for changing the coupler.

The electrophotographic photoreceptor of the present invention has an electrophotographic photosensitive layer containing one or more disazo compounds represented by the above general formula. Various types of electrophotographic photoreceptors are known, and the electrophotographic photoreceptor of the present invention may be any type of photoreceptor, but it usually has an electrophotographic photoreceptor structure of the type exemplified below. .

+11 An electrophotographic photosensitive layer comprising a disazo compound dispersed in a binder or a charge carrier transport medium is provided on a conductive support.

(2) A charge carrier generation layer containing a disazo compound as a main component is provided on a conductive support, and a charge carrier transporting medium layer is provided thereon.

The disazo compound of the present invention acts as a photoconductive substance,
When light is absorbed, charge carriers are generated with extremely high efficiency, and the generated charge carriers can be transported using a disazo compound as a medium, but it is more effective to transport them using a charge carrier transporting compound as a medium. It is.

To create an electrophotographic photoreceptor of type (1), fine particles of a disazo compound are dispersed in a binder solution or a solution containing a charge carrier transporting compound and a binder, and this is applied onto a conductive support and dried. . The thickness of the electrophotographic photosensitive layer at this time is 6 to 30 μm, preferably 5 to 20 μm.
μ is good.

To create an electrophotographic photoreceptor of type (2), a disazo compound is vacuum-deposited on a conductive support, or dissolved in a solvent such as amine and coated, or fine particles of a disazo compound are coated on a conductive support with a suitable solvent or If necessary, it can be obtained by dispersing it in a solvent in which a binder has been dissolved, coating and drying, and then coating and drying a solution containing a charge carrier transport compound and a binder thereon. The thickness of the disazo compound layer serving as the charge carrier generation layer at this time is preferably 4 μm or less, preferably 2 μm or less, and the thickness of the charge carrier transport medium layer is preferably 6 to 60 μm, preferably 5 to 20 μm.

The disazo compound used in the photoreceptors of types (1) and (2) is used after being ground to a particle size of 5 μm or less, preferably 2 μm or less, using a dispersing machine such as a ball mill, sand mill, or vibration mill.

If the amount of the disazo compound used in the electrophotographic photoreceptor of type (1) is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor, the strength of the electrophotographic photosensitive layer will be weakened, and the electrophotographic photoreceptor will have poor sensitivity. The ratio of the disazo compound in the layer to the binder is preferably 0.01 to 2 times, preferably 0.05 to 1 part by weight, and the ratio of the charge carrier transport compound added as necessary is 0 to the binder. .1~2
It is preferably in the range of 0.6 to 1.6 times the weight of stored goods. In the case of a charge carrier transporting compound which itself can be used as a binder, the disazo compound is preferably added in an amount of 0.01 to 0.5 times the amount of the disazo compound.

In addition, when forming a disazo compound-containing layer which is a charge carrier generating layer and a layer in an electrophotographic photoreceptor of type (2), the amount of disazo compound used relative to the binder resin is 1.
Preferably, it is more than twice the weight, and if it is less than that, sufficient photosensitivity cannot be obtained. The proportion of the charge carrier transport compound in the charge carrier transport medium is preferably 0.2 to 2 times 16 times, preferably 0.6 to 1.6 times the weight of the binder. If a polymeric charge carrier transport compound is used which itself can be used as a binder, no other binder can be used.

When producing the electrophotographic photoreceptor of the present invention, additives such as a plasticizer or a sensitizer may be used together with the binder.

The conductive support used in the single-child photographic photoreceptor of the present invention includes metal plates such as aluminum, copper, curved lead, etc.
A conductive material such as aluminum or SnO□ is applied to a plastic sheet or film such as polyester.
A coated or dispersed coated paper, or conductive treated paper is used.

Examples of the binder include condensed yarns such as polyamide, polyurethane, polyester, epoxy resin, polycarbonate, etc. (vinyl polymers such as 91 fat, boribi, nilketone, polystyrene, 2-N-vinylcarbazole, and polyacrylamide). However,
Any insulating and adhesive resin can be used.

Plasticizers include biphenyl, chlorinated biphenyl, o-f-ruphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol tucrate, dioctyl phthalate,
Triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene,
Examples include dilauryl thiodipropionate, 3,5-dinitrosalicylic acid, various fluorohydrocarbons, and the like.

In addition, silicone oil or the like may be added to improve the surface properties of the electrophotographic photoreceptor.

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

Compounds that transport charge carriers are generally classified into two types: compounds that transport electrons and compounds that transport holes, and both can be used in the electrophotographic photoreceptor of the present invention. Compounds that transport electrons include compounds that have an electron-withdrawing group, such as EVA2,4.7-)! J nitro 9-fluorenone, 2゜4,5.7-tetranitro-
9-fluorenone, 9-dicyanomethylene-2,4,7
−)! J nitrofluorenone, 9-dicyanomethylene-2,4,5,7-tetranitrofluorenone, tetranitrocarbazole chloranil, 2,3-cyclo-5
．． Examples include 6-dicyanobanzoquinone, 2,4,7-dolinitro-9,10-phenanthrenequinone, tetrachlorophthalic anhydride, tetracyanoethylene, and tetracyanoquinodimethane.

Compounds that transport holes include compounds having a single-donating group, such as polymers (11 Japanese Patent Publication No. 34-1989).
Pyrivinylcarbazole and derivatives thereof as described in JP-A No. 10966, (2) Japanese Patent Publication No. 18674-1986, Japanese Patent Publication No. 46-1
Polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4-(4'-dimethylaminophenyl)-5-phenyl-oxazole, yy described in Publication No. 9192
Vinyl polymers such as v-s-vinyl-N-ethylcarbazole - (3) Polymers such as polyacenaphthylene, polyindene, coelectric polymers of acenaphthylene and styrene, etc. described in Japanese Patent Publication No. 19193-1983, ( 4) Tokuko Sho 5
Condensation resins such as hyalene-formaldehyde m resin, brompyrene-formaldehyde 9 resin, and ethylcarbazole-formaldehyde resin described in Japanese Patent No. 6-13940, (y) described in U.S. Patent No. 6,112,197, etc. Triazole derivative, +C+ Oxadiazole cast conductor described in U.S. Pat. No. 5615402, No. 38
No. 20989, No. 3542544, Special Publication No. 45-55
No. 5, JP 51-10986, JP 51-932
No. 24, Japanese Patent Application No. 1988-88272, Japanese Patent Application No. 1982-78
Specification No. 968,! Polyarylalkane derivatives described in Samurai Publication No. 55-108667, Japanese Patent Application Publication No. 55-156955, Japanese Patent Application Publication No. 56-36656, etc.
-75854, JP-A No. 55-88064, JP-A-Sho 5
5-88065, JP-A-49-105537, JP-A-55-51086, JP-A-56-8L1051+t
, Japanese Patent Publication No. 56-88141, Japanese Patent Publication No. 57-45
No. 545, JP-A-54-112637, JP-A-55-
Pyrazoline derivatives and pyrazolone conductors described in Patent No. 74546, publications, etc.

60) U.S. Patent No. 3,615,404, Ministry of Specification, 1973
-10105, JP-A-54-86465, JP-A-5
4-110836, JP 54-119925, JP 46-6712, and JP 47-28336 Fr, (11) U.S. Pat. 35
No. 702, West German Special IV'F (DAS) 11105
No. 18, U.S. Patent No. 3180703, U.S. Patent W1 No. 3
No. 240597, U.S. Patent No. 3658520, U.S. W[No. 4232103, U.S. Pat. No. 417596]
No. 1, U.S. Patent No. 4012376, JP-A-55-14
No. 4250, JP-A No. 56-119132, Special Publication No. 39-Sho.
-27577, JP-A No. 56-22437, arylamine derivatives described in publications, etc., amino-purchased chalcone derivatives described in U.S. Pat. No. 3,526,501, etc. (1'3) U.S. Patent No. N,N-bicarbasil derivatives described in US Pat. No. 3,542,546, etc., (Ill) oxazole derivatives described in US Pat. Derivatives, (16) Fluorenone derivatives described in JP-A-54-110867, etc. (17) U.S. Special Agreement No. 6717462, JP-A-54-
No. 59146 (corresponding to U.S. Pat. No. 4,150,987),
JP 55-52063, JP 55-52064, Samurai JP 55-46760, JP 55-85495
Issue, ll'l・muiH 1974--'i! J”B’ 49
No. 5, No. 11v Gansho 56-66B62, etc. These include hydrazone derivatives.

In addition, in the present invention, the compound that transports the military tae complex is f
It is not limited to the compounds listed in Il to Oa, and all hitherto known charge carrier transport compounds can be used. These charge transport materials can also be used in combination with 2s or more, depending on the case.

In the photoreceptor obtained as described above, an adhesive layer or barrier layer may be provided between the conductive support and the photosensitive layer, if necessary. Materials used for these M include polyamide 9, nitrocellulose, aluminum oxide, etc., and the j9 thickness of these layers is preferably 1 μm or less.

The electrophotographic photoreceptor of the present invention has been described in detail above, and the electrophotographic photoreceptor of the present invention generally has the characteristics of high sensitivity and excellent durability.

The electrophotographic photoreceptor of the present invention can be widely applied in fields such as photoreceptors for printers using lasers and cathode ray tubes as light sources, as well as electrophotographic copying machines.

The photoconductive composition containing the disazo compound of the present invention can be applied as a photoconductive layer of an image pickup tube of a video camera, or on the entire surface of a one-dimensional or two-dimensional array of semiconductor circuits for performing known signal transfer or scanning. It can be used as a photoconductive layer of a solid-state image sensor having a light-receiving layer (light-guiding 1L layer). Also, A. K. Ghosh.

Tom Feng, J. Appl, Phys., 49
(1,2) 5982 (197B), it can also be used as a photoconductive layer in solar cells.

Further, the trisazo compound of the present invention can be used in Japanese Patent Publication No. 67-171
No. 62, JP-A-55-19066, JP-A-55-16
As disclosed in each publication No. 1250 and the specification of each application No. 56-66579, alkali-soluble resins such as phenolic resins are used together with the aforementioned carrier-transporting compounds such as oxysiazole M4 and hydrazone derivatives. Dispersed in a liquid and coated on a 4'M support such as aluminum1
], After drying, by image exposure, toner development, and etching with aqueous alkali solution, a printing plate with high WC image power, high durability, and high sensitivity can be obtained, and a printed circuit can also be created.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples. In the examples, "part" indicates "inside part".

Example 1 1 part of a disazo compound (IG), 5 parts of 4,4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane, and 5 parts of bisphenol A polycarbonate were added to 95 parts of dichloromethane, and the mixture was milled in a ball mill. The coating solution was prepared using a wire round rod and applied onto a conductive transparent support (100 μm polyethylene terephthalate film with a vapor-deposited film of indium oxide on the surface. Surface resistance: 10Ω). The mixture was coated and dried to prepare an electrophotographic photoreceptor having a single-layer electrophotographic photosensitive layer with a thickness of about 8 μm.

This electrophotographic photoreceptor was charged to +400V by +5KV corona discharge using an electrostatic copying paper tester (manufactured by Kawaguchi Electric Co., Ltd., model 5P-428), and then its surface was charged with a tungsten lamp with a color temperature of 30,000. 4
We irradiated the lux with light as in 1 and determined the time required for the surface potential to attenuate to half of the initial surface potential, and measured the half-decreased light output E50 (Lux, 5ee).7 Q (Lux).

5ec);r was there. The E50 value after repeating the two steps of charging and exposure 6000 times also hardly changed.

Examples 2 to 81 Disazo compounds (1A), (2 people), (6A), (4A), (5A) were used instead of disazo compound (1G), respectively.
), (11A), (16A), (48A), (56A)
, (61A), (1B), (2B), (3B), (4B
), (5B), (25B), (26B), (49B),
(54B), (62B), (1G), (6G), (4G
), (5G), (11G), (13G), (250),
(48C), (55G), (66G), (1D), (2
D), (4D), (5D), (1roD), (181))
, <26D), (49D), (56D), C640),
(1F), (2E), (5E), (11E), (16E
), (19F), (29K), (44E), (57E)
, (65E), (1F), (6F), (5F), (11
F'), (16F), (26F), (29F), (45
F), (56F), (61F), (2G), (6G)
, (4G), (5G), (110), (13G), (2
5G), (2<SG), (48G), <54G), (6
2G>, (1H), (6H), (5H), (8H), (
2roH), (25H), (47H), (57H), (6
6H), An electrophotographic photoreceptor having a base layer structure was prepared in the same manner as in Example 1 except that
The half-reduction exposure due to positive charging was measured and the values shown in Table 2 were obtained.

Continuation of the second coating Example 82 5 g of disazo compound (2G) and polyvinyl butyral resin (degree of butyralization 63 mol%) 2J9 were added to 1 ethanol 1
After dispersing with a solution dissolved in 00fflA in a ball mill for 20 hours, using a wire round rod, conductive transparent support (100 μm polyethylene terephthalate film with a vapor deposited aluminum film on the surface. Surface electrical resistance 103Ω) It was coated on top and dried to form a charge generation layer with a large thickness.

Next, on the charge generation layer, a solution of 2 parts of p-(diphenylamino)penzaldehy)sN/-methyl-N'-phenylhydrazone and 4 parts of polycarbonate to bisphenol dissolved in 60 parts of dichloromethane was added. The mixture was applied and dried using a wire round rod to form a charge transport layer having a thickness of 8 μm, thereby producing an electrophotographic photoreceptor having a two-layer electrophotographic photosensitive layer.

After this photoreceptor was charged to -400V by corona discharge of -5KV, the half-decrease exposure was measured, and the Eso was 15
(lux, 5ec) C Examples 86 to 146 Disazo compound (1 person), (3A), (5A), (7A), (12
A), (43A), (54A), (62A), (1B)
, (2B), (15B), (17B), (27B), 4
5B), (56B), (61B), (2C), (4G)
, (6G), (10G), (67G), C4BG>, (
'55G), C64G), (1D), (4D), (5I
)), (8D), (25D), (46D), (57D)
, (63D), (1E), (2E), (7E), (16
E), (29E), (47E), (53E), (<55
E), (2F), (6F), (9F), (12F) (3
8F), (49F), (58F), (66F), (IG
), (4G), (18G), (19G), (39C,)
, (48G), (60G), (61G), (2H), (
4H), (6H), (7H), (18H), (49H)
, (56H), and (63H) were used in the same manner as in Example 82 to prepare a two-layer electrophotographic photoreceptor.
Continuation of Table 6 Example 147 As a charge transport layer, instead of p-(diphenylamino)banzaldehyde)N'-mediQ-N'-phenylhydrazone, 2,4.7- ) A charge transport layer having a thickness of 12 μm was formed on a charge generation layer having a thickness of 1 μm in the same manner as in Example 82 except that 4 parts of dinitro-9-fluorophore was used.

This electrophotographic photoreceptor is heated to +6 by corona discharge of +5KV.
When charged to 00■ and measured 50, 23 (1
ux-sec).

Examples 148 to 179 Disazo compounds (2 people), (50A), (57A), (62A), respectively, instead of disazo compound (2G)
, (10B), (46B), (55B), (66B),
(15G), (51C), (540), (61C), (
7D), (4roD), (56D), (64D), (14
E), (52K), (59F), (66E), (11F
), (48F), (60F), (65F), (5(1,
), (48G), (56G), (61G), (11H)
, (48H'), (55H), and (62H) (*) A two-layer electrophotographic photoreceptor was prepared in the same manner as in Example 147 except that E5o was measured.

The results are shown in Table 4.

Table 4 Continuation of Table 4 Example 180 1 part of disazo compound (2G) and bisphenol A
Add 1 part of polycarbonate and 25 parts of dichloromethane to 25 parts of dichloromethane, grind and mix in a ball mill to prepare a solution, and apply this coating solution to a conductive transparent support (the surface of a 100 μm polyethylene terephthalate film) using a wire round rod. An electrophotographic photoreceptor having a single-layer electrophotographic photosensitive layer with a thickness of about 9 μm was obtained by coating and drying a film on which a vapor-deposited film of indium oxide (surface resistance: 10 3 Ω) was provided.

This electrophotographic photoreceptor is heated to +4 by corona discharge of +5KV.
After charging to 50V, E50 was measured and found to be 47 (
lux, 5ec).

Examples 181 to 212 Disazo compounds (6A), (51A), (56A), (61A) were used instead of disazo compounds (2(,), respectively).
), (12B), (45B), (54B), (62B)
, (18G), (480), (58C), (630),
17D), (44D), (53D), (63D), (2
1E), (46E), (55E), (62E), (24
F), (44F), (57F), (64F), (19G
), (51(,), (54G), (61G), (13H
), (45H), (59)(), (64)1) A single-layer electrophotographic photoreceptor was prepared in the same manner as in Example 180, except that E. was measured. The results are shown in Table 5.

Table 5 Continuation of Table 5 Example 188 1 part of trisazo pigment (11G) and p-(:)phenylamino)banzaldehyde N'- used in Example 7
Add 1 part of methyl-N'-phenylhydrazone and 6 parts of m-cresol formaldehyde resin to 30 parts of ethylene glycol monomethyl ether, grind and mix in a ball mill, and reduce the coating solution to a thickness of about 0.251111. J
A sample with a height of about 6 μm was prepared.

Next, corona discharge was applied to this sample so that the voltage at surface 1 was 500 V at 11.4 points, and a negative image was exposed to tungsten light (500 lux seconds). When reversal development was carried out using a printing press (manufactured by Paper Manufacturing Co., Ltd.), a very clear positive image could be obtained on the original printing plate. This printing original plate was immersed for 1 minute in a 10-fold diluted solution of Etching 1DP-1 (manufactured by Fuji Photo Film Co., Ltd.; sodium silicate aqueous solution) to remove the photosensitive layer in the subdivisions (non-image areas) to which toner was not attached. Dissolved and removed. As a result, the pigment in the non-image area was easily removed together with the binder, and a printing plate with a clear image could be formed.

[Brief explanation of drawings]

Figures 1 and 2 show disazo compounds (2C) and (
11G) infrared absorption spectrum (KBr method). Procedural amendment 1982+ [July 2nd, Mr. Kazuo Wakasugi, Commissioner of the Patent Office (Mr. Patent Office Examiner) 1, Indication of the case, Patent Application No. 101341 of 1981 2, Name of the invention: Disazo compound, photoconductive material containing the same Composition and electrophotographic photoreceptor 3, relationship with the case of the person making the amendment: Name of patent applicant: Fuji Photo Film Co., Ltd. (Shipping date: 1999)
Month, day) 6. Number of inventions increased by amendment 0 7. Subject of amendment a) Amend the following on page 22, line 6. b) Delete [(31A) J on the last line of page 28. C) After page 156, line 9: “(5) JP-A-56-90833, JP-A-56-1615
various triphenylmethane polymers described in No. 50 specification. d) Numbers from page 157, line 1 to page 159, line 10: ``(From May, rc171J may be ``+61J.''
"vomit," he corrected. e) Table 2 (continued) where [, Japanese Patent Application Laid-Open No. 57-64244] is added after "Japanese Patent Application No. 56-33832" on page 159, line 15.

Claims (3)

[Claims] (1) A disazo compound represented by the following general formula [1]. [1] X is bonded to the benzene ring in the above formula to which a hydroxy group and Y are bonded to form an aromatic ring such as a naphthalene ring or anthracene ring, or an indole ring, a carbazole ring, a carbazole ring, or a dibenzofuran ring. Heterocycles such as rings (all rings are substituted or unsubstituted, R represents an alkyl group, phenyl group, or a substituted product thereof, R is a hydrogen atom, a lower alkyl group, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an aryl group) represents an oxycarbonyl group or a substituted or unsubstituted amino group; R and R are an alkyl group; an aromatic ring group such as a phenyl group;
It represents a heteroaromatic ring group such as a divanzofuranyl group or a carbazolyl group, or a substituent thereof, and R represents a hydrogen atom, an alkyl group, a phenyl group, or a substituent thereof. (2) A photoconductive composition characterized by containing a disazo compound represented by the following general formula [1]. B-N=NGCHzu)1-A-cH=cH@N=N
-B [1] In the above general formula, X is fused with the benzene ring in the above formula to which a hydroxy group and Y are bonded to form an aromatic ring such as a naphthalene ring or anthracene ring, or an indole ring or a carbazole ring. Heterocycles such as , penzocarno dizole ring, dibenzofuran ring (
Either ring may be substituted or unsubstituted. R represents an alkyl group, a phenyl group, or a substituted product thereof, and R2 represents a hydrogen atom, a lower alkyl group, or a carboxylic acid group. represents a saponyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a substituted or unsubstituted amino group, R and R are an alkyl group; an aromatic ring group such as a phenyl group;
It represents a heteroaromatic ring group such as a dibenzofuranyl group or a carbazole ring, or a substituent thereof, and R represents a hydrogen atom, an alkyl group, a phenyl group, or a substituent thereof. (3) In the above general formula, A is any one of the groups below. X is condensed with the benzene ring in the above formula to which a hydroxy group and Y are bonded to form an aromatic ring such as a naphthalene ring or anthracene ring, or an indole ring, a carbazole ring, a benzocarbazole ring, a dibenzofuran ring, etc. represents an atomic group necessary to form a heterocycle (both rings may be substituted or unsubstituted), R represents an alkyl group, a phenyl group, or a substituted product thereof, R represents a hydrogen atom, a lower alkyl group , represents a carbamoyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, or a substituted or unsubstituted amino group, R3 and R are an alkyl group; an aromatic ring group such as a phenyl group; a dibenzofuranyl group , a heteroaromatic ring group such as a carbazolyl group, or a substituted product thereof, and R represents a hydrogen atom, an alkyl group, a phenyl group, or a substituted product thereof.