JP2003176270A - Enamine compound, electrophotographic photoreceptor and image forming apparatus using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic light having high charge potential, high sensitivity, sufficient photoresponsiveness in a low-temperature environment and a high-speed process, excellent durability, and usable for an electrophotographic photoreceptor. Provided are an enamine compound which is a conductive material, an electrophotographic photosensitive member using the same, and an image forming apparatus. SOLUTION: An enamine compound having a structure represented by the following general formula (1) is synthesized. Such an enamine compound is contained as a charge transport material 3 in the charge transport layer 6 on the conductive support 1 to produce an electrophotographic photoreceptor. Embedded image (Wherein, Ar ¹ and Ar ² each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Z represents a ring together with Ar ¹ , a carbon atom and Ar ² And W represents an atomic group necessary for forming a ring together with a nitrogen atom. R ¹ represents a hydrogen atom or an alkyl group which may contain a substituent.)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic photoconductive material,
The present invention relates to an electrophotographic photoreceptor and an image forming apparatus using the same.

[0002]

2. Description of the Related Art In recent years, organic photoconductive materials have been extensively researched and developed and are used not only for electrophotographic photoreceptors (hereinafter also simply referred to as "photoreceptors"), but also for electrostatic recording elements, sensor materials, organic materials. Application to EL (EL: Electroluminescent) devices and the like has begun. Further, the use of the electrophotographic method using the organic photoconductive material is not limited to the field of the copying machine, and is expanded to the fields of the printing plate material, the slide film, the microfilm, etc. in which the photographic technology has been conventionally used. laser,
LED (Light Emitting Diode), CRT (Cathode Ra)
It is also applied to high-speed printers that use the (Y Tube) as a light source. Therefore, the demands for organic photoconductive materials and electrophotographic photoreceptors using them are becoming high and wide.

Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer containing an inorganic photoconductive material such as selenium, zinc oxide or cadmium as a main component has been widely used. The inorganic photoconductor has some basic characteristics as a photoconductor, but has problems such as difficulty in film formation, poor plasticity, and high manufacturing cost. Further, the inorganic photoconductive material is generally highly toxic, and there are great restrictions in manufacturing and handling.

On the other hand, an organic photoconductor using an organic photoconductive material has a good film-forming property and is excellent in flexibility, is light in weight and has good transparency, and is suitable for a suitable sensitizing method. Therefore, it is gradually developed as the main force of electrophotographic photoreceptors because it has advantages such as easy design of a photoreceptor having sensitivity in a wide wavelength range. Although the conventional organic photoreceptor has drawbacks in sensitivity and durability, it is remarkably improved by a function-separated electrophotographic photoreceptor in which a charge generating function and a charge transporting function are shared by different substances. Such a function-separated type photoreceptor has a wide range of material selection for each of the charge generating substance and the charge transporting substance, and also has an advantage that an electrophotographic photoreceptor having arbitrary characteristics can be prepared relatively easily.

Of these, as the charge generating substance which is in charge of the charge generating function, phthalocyanine pigments, squarylium dyes, azo pigments, perylene pigments, polycyclic quinone pigments, cyanine dyes, squaric acid dyes, pyrylium salt dyes, etc. , Various materials have been studied, and various materials having strong light resistance and large charge generation ability have been proposed.

On the other hand, examples of the charge-transporting substance which is a substance in charge of the charge-transporting function include, for example, Japanese Patent Publication No. 52-4188
Compounds disclosed in Japanese Patent Laid-Open No. 54-591
43, JP-A-54-150128, JP-B-55-42380 and JP-A-55-52063.
Compounds disclosed in Japanese Patent Publication No. 58-323
72 and JP-A-2-190862, the triphenylamine compounds disclosed in JP-A-54-15195.
The stilbene compounds disclosed in JP-A No. 5 and JP-A No. 58-198043 are known. Recently, pyrene derivatives, naphthalene derivatives, and terphenyl derivatives disclosed in JP-A-7-48324, which have a condensed polycyclic hydrocarbon system in their central mother nucleus, have been developed.

These charge transport materials are (1) stable to light and heat, (2) stable to ozone, NO _x , nitric acid, etc. generated by corona discharge, (3) ) It is required to have a high charge transport ability, (4) high compatibility with an organic solvent and a binder, and (5) easy and inexpensive production. However, conventional charge transport materials satisfy some of the above requirements, but have not yet satisfied all of them at a high level.

In particular, it is strongly required to have a high charge transporting ability. That is, when the charge transport layer formed by dispersing the charge transport substance together with the binder resin is the surface layer of the photoconductor, when it is mounted on a copying machine or a laser beam printer and used, a functional member such as a cleaning blade or a charging roller. It is forced to remove a part of it. In order to improve the durability of copying machines and laser beam printers, a strong surface layer is required for those functional members. Therefore, if the content of the binder resin in the charge transport layer is increased in order to strengthen the surface layer and improve the durability, the photoresponsiveness will decrease. This is because the charge transport material has a low charge transport ability. If the photoresponsiveness is poor, the surface potential of the photoconductor will be repeatedly used in a state where it has not been sufficiently attenuated, and the potential change due to the increase in the residual potential will increase, leading to an adverse effect such as early deterioration of image quality. Accompany. Therefore, there is a demand for an organic photoconductive material having a high charge transporting ability in order to secure sufficient responsiveness.

In recent years, electrophotographic devices such as digital copying machines and printers have become smaller and faster, and it has been required that the photoconductor characteristics have higher sensitivity corresponding to the higher speed. Transport capacity is required.

Further, as a characteristic of the photoconductor, it is required that the sensitivity does not decrease even when used in a low temperature environment.

As a charge transport material satisfying such requirements, the mobility is higher than that of conventional charge transport materials.
The enamine compounds disclosed in JP-A-51162 and JP-A-10-69107 can be mentioned. However, its performance is not sufficient, it is not possible to meet all the above requirements, and a charge transport material that realizes all the required properties has not been obtained.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor having a high charging potential, high sensitivity, sufficient photoresponsiveness in a low temperature environment and a high speed process, and excellent durability. An object is to provide an enamine compound that is an organic photoconductive material that can be used as a sensor material, an EL element, an electrostatic recording element, and the like, an electrophotographic photoreceptor and an image forming apparatus using the same.

[0013]

The present invention is an enamine compound represented by the following general formula (1).

[0014]

[Chemical 7]

(In the formula, Ar ¹ and Ar ² each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Z represents a ring together with Ar ¹ , a carbon atom and Ar ^2. W represents an atomic group necessary for forming R. W represents an atomic group necessary for forming a ring with a nitrogen atom.
¹ represents a hydrogen atom or an alkyl group which may have a substituent. )

According to the present invention, an enamine compound, which is an organic photoconductive material having high charge mobility, can be obtained by having the structure represented by the general formula (1), particularly the cyclic enamine structure. When an enamine compound having such a high mobility is used as an organic photoconductive material in an electrophotographic photoreceptor, a sensor material, an EL element, an electrostatic recording element, or the like, a device having excellent responsiveness can be provided.

Further, the present invention is characterized in that the enamine compound represented by the general formula (1) is represented by the following general formula (2).

[0018]

[Chemical 8]

(In the formula, Ar ⁵ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
X represents an atomic group necessary for forming a ring with Ar ⁵ and a nitrogen atom. Ar ¹ , Ar ² , R ¹ and Z have the same meaning as defined in the general formula (1). )

Further, the present invention is characterized in that the enamine compound represented by the general formula (1) is represented by the following general formula (3).

[0021]

[Chemical 9]

(In the formula, Ar ³ and Ar ⁴ each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Y represents a ring together with Ar ³ , a nitrogen atom and Ar ^4. The atomic groups necessary for formation are shown below: Ar ¹ ,
Ar ² , R ¹ and Z have the same meaning as defined in the general formula (1). )

According to the present invention, an enamine compound, which is an organic photoconductive material having a particularly high charge mobility, is obtained by having the structure represented by the general formula (2) or (3), particularly the cyclic enamine structure. be able to. When an enamine compound having such a high mobility is used as an organic photoconductive material in an electrophotographic photoreceptor, a sensor material, an EL element, an electrostatic recording element, or the like, a device having excellent responsiveness can be provided.

Further, the present invention is characterized in that the enamine compound represented by the general formula (2) is represented by the following general formula (4).

[0025]

[Chemical 10]

(In the formula, each of a, b and f may have a C1-5 alkyl group which may have a substituent, an C1-3 alkoxy group which may have a substituent, or a substituent. A dialkylamino group containing an alkyl chain having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom is shown, and j, m and n are integers of 1 to 4, provided that j, m and n are 2 or more, Corresponding plural a, b and f may be the same or different and may form a ring with each other V is an atomic group necessary for forming a ring, an alkylene chain which may contain a substituent, a substituent Represents an unsaturated alkylene chain which may contain a group, a hetero atom which may contain a substituent, or an alkylene chain which contains a hetero atom or an unsaturated alkylene chain which may contain a substituent, wherein R ¹ and X are each represented by the above general formula ( 1) and ( The same meaning as defined in).)

Further, the present invention is characterized in that the enamine compound represented by the general formula (2) is represented by the following general formula (5).

[0028]

[Chemical 11]

(In the formula, each of a, b and e may have a C1-5 alkyl group which may have a substituent, an C1-3 alkoxy group which may have a substituent, or a substituent. A dialkylamino group having a good C1 to C3 alkyl chain, a halogen atom or a hydrogen atom is shown, and i is 1 to 8
, And m and n are integers of 1 to 4. However,
When i, m and n are 2 or more, a plurality of corresponding a, b
And e may be the same or different and may form a ring with each other. V is a group of atoms necessary for forming a ring, which may contain an alkylene chain which may have a substituent, an unsaturated alkylene chain which may have a substituent, a hetero atom which may have a substituent, or a substituent. Represents an alkylene chain containing a hetero atom or an unsaturated alkylene chain. R ¹ has the same meaning as defined in the general formula (1). )

Further, the present invention is characterized in that the enamine compound represented by the general formula (3) is represented by the following general formula (6).

[0031]

[Chemical 12]

(In the formula, a, b, c and d are respectively substituted
An alkyl group having 1 to 5 carbon atoms which may contain a group, a substituent
It may contain an alkoxy group having 1 to 3 carbon atoms or a substituent.
Dialkyl containing an alkyl chain having 1 to 3 carbon atoms
An amino group, a halogen atom or a hydrogen atom, k,
l, m, and n show the integer of 1-4. However, k,
When l, m and n are 2 or more, a plurality of corresponding a,
b, c and d may be the same or different and may form a ring with each other.
You may form. V and T each form a ring
A group of atoms required for alkylene which may contain a substituent
Chain, unsaturated alkylene chain which may contain a substituent, substituent
May contain a hetero atom, or may contain a substituent.
An alkylene chain containing a hetero atom or an unsaturated alkyl group
The xylene chain is shown. R ¹Is defined in the above general formula (1)
It is synonymous with what was done. )

According to the present invention, the general formula (4),
By having the structure represented by (5) or (6), an enamine compound which is an organic photoconductive material having high charge mobility can be obtained at low cost. When an enamine compound having such a high mobility is used as an organic photoconductive material in an electrophotographic photoreceptor, a sensor material, an EL element, an electrostatic recording element, or the like, a device having excellent responsiveness can be provided.

The present invention is also an electrophotographic photoreceptor characterized in that the photosensitive layer provided on a conductive support contains the above-mentioned enamine compound as a charge transporting substance.

According to the present invention, the above general formulas (1) to
By incorporating the enamine compound having high charge mobility represented by (6) into the photosensitive layer as a charge transporting substance,
It is possible to obtain an electrophotographic photosensitive member having high sensitivity and having sufficient photoresponsiveness even in a low temperature environment and a high speed process. Further, by using such an enamine compound having high mobility, a binder resin can be added at a higher ratio than in the case of using a conventionally known charge transporting substance, and a highly durable electrophotographic photosensitive material having improved printing durability. You can get the body.

Further, the present invention is characterized in that the photosensitive layer has a laminated structure having at least a charge generating layer containing a charge generating substance and a charge transporting layer containing the charge transporting substance.

According to the present invention, the general formulas (1) to (1) to
By containing the enamine compound represented by (6) having a high charge mobility in the charge transport layer, it is possible to provide a laminated electrophotographic photoreceptor having high sensitivity and excellent durability.

Further, the present invention is characterized in that an intermediate layer is provided between the conductive support and the photosensitive layer.

According to the present invention, by providing an intermediate layer between the conductive support and the photosensitive layer, a protective function of the photosensitive layer is provided, and at the same time, the adhesiveness between the photosensitive layer and the conductive support and the photosensitivity. The coatability of the layer can be improved. Further, it is possible to prevent the injection of charges from the conductive support to the photosensitive layer and the generation of interference fringes which are considered to be mainly caused by the reflection of the laser light on the substrate.

The present invention is also an image forming apparatus including the electrophotographic photosensitive member.

According to the present invention, by providing the electrophotographic photoreceptor containing the above-mentioned enamine compound as a charge transporting substance, it is possible to obtain high sensitivity and excellent durability, and to use it in a low temperature environment and a high speed process. It is also possible to provide an image forming apparatus whose electric characteristics are not deteriorated.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION The enamine compound of the present invention is represented by the following general formula (1).

[0043]

[Chemical 13]

In the general formula (1), Ar ¹ and Ar ² each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Specific examples include aryl groups such as phenyl, tolyl, methoxyphenyl, naphthyl and biphenyl, and thienyl,
Mention may be made of heterocyclic groups such as thiazolyl, benzofuryl, benzothiophenyl and N-methylindolyl.

In the general formula (1), Z is A
The atomic groups necessary for forming a ring with r ¹ , carbon atom and Ar ² are shown. Specific examples include methylene chains, alkylene chains such as ethylene chains and dimethylmethylene chains,
Examples thereof include unsaturated alkylene chains such as vinylene chains and propenylene chains, and nitrogen atoms having a substituent such as a sulfur atom, an oxygen atom, a selenium atom, and an alkyl group, and a hetero atom such as a silicon atom.

In the above general formula (1), W represents an atomic group necessary for forming a ring with a nitrogen atom. Specific examples include alkylene chains such as ethylene chains and propylene chains, unsaturated alkylene chains such as vinylene chains and propenylene chains, alkylene chains containing heteroatoms such as oxymethylene chains, and heteroatoms such as thiovinylene chains. An unsaturated alkylene chain etc. can be mentioned. Specific examples of the ring formed by W together with the nitrogen atom include heterocycles such as a pyrrole ring, an oxazole ring, a thiazole ring and an imidazole ring. These rings may have a substituent and may be condensed with other rings to form a condensed heterocycle such as an indole ring, a carbazole ring and a phenoxazine ring.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group which may have a substituent.
Specific examples thereof include an alkyl group such as methyl, ethyl, n-propyl, isopropyl and trifluoromethyl, and a hydrogen atom.

The enamine compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) or (3).

[0049]

[Chemical 14]

[0050]

[Chemical 15]

In the above general formula (2), Ar ⁵ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Specific examples include aryl groups such as phenyl, tolyl, methoxyphenyl, naphthyl and biphenyl, and heterocyclic groups such as thienyl, thiazolyl, benzofuryl, benzothiophenyl and N-methylindolyl.

In the general formula (2), X is Ar.
^A group of atoms necessary for forming a ring with ⁵ and a nitrogen atom is shown. Specific examples include methylene chains, alkylene chains such as ethylene chains and dimethylmethylene chains, unsaturated alkylene chains such as vinylene chains and propenylene chains, alkylene chains containing a hetero atom such as oxymethylene chains,
And an unsaturated alkylene chain containing a hetero atom such as a thiovinylene chain. Specific examples of the ring formed by X together with Ar ⁵ and the nitrogen atom include heterocycles such as indole ring, benzoxazole ring and benzothiazole ring. These rings may have a substituent and may be condensed with other rings to form a condensed heterocycle such as a carbazole ring.

In the general formula (2), Ar ¹ ,
Ar ² , R ¹ and Z have the same meaning as defined in the general formula (1).

In the general formula (3), Ar ³ and Ar ⁴ each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Specific examples include aryl groups such as phenyl, tolyl, methoxyphenyl, naphthyl and biphenyl, and thienyl,
Mention may be made of heterocyclic groups such as thiazolyl, benzofuryl, benzothiophenyl and N-methylindolyl.

In the general formula (3), Y is A
r³, Nitrogen atom and Ar^FourRequired to form a ring with
The necessary atomic groups are shown. Specific examples include a methylene chain and ethylene.
Alkylene chains such as len chains and dimethylmethylene chains,
Unsaturated alkyles such as vinylene and propenylene chains
Alkynes containing heteroatoms such as
Unsaturation containing heteroatoms such as len chains and thiovinylene chains
Alkylene chain, oxygen atom, sulfur atom, selenium atom
And a nitrogen atom having a substituent such as an alkyl group,
Examples include heteroatoms such as silicon atoms.
It Y is Ar ³, Nitrogen atom and Ar^FourTo form with
Specific examples of the ring include a phenoxazine ring and phenothiazine ring.
Heterocycles such as an azine ring can be mentioned.

In the general formula (3), Ar ¹ ,
Ar ² , R ¹ and Z have the same meaning as defined in the general formula (1).

Specific examples of the compound contained in the enamine compound represented by the general formula (2) include enamine compounds represented by the following general formulas (4) and (5).

[0058]

[Chemical 16]

[0059]

[Chemical 17]

Specific examples of the compound contained in the enamine compound represented by the general formula (3) include enamine compounds represented by the following general formula (6).

[0061]

[Chemical 18]

In the general formula (4), a, b and f are each an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms which may have a substituent, and a substituent. Represents a dialkylamino group containing an alkyl chain having 1 to 3 carbon atoms which may contain a group, a halogen atom or a hydrogen atom, and j, m and n each represent an integer of 1 to 4. However, when j, m and n are 2 or more, a plurality of corresponding a, b and f may be the same or different and may form a ring with each other.

In the general formula (4), V is a group of atoms necessary for forming a ring, which includes an alkylene chain which may have a substituent, an unsaturated alkylene chain which may have a substituent, and a substituent. Represents an alkylene chain or an unsaturated alkylene chain containing a hetero atom which may be substituted or a hetero atom, which may contain a substituent.

In the general formula (4), R ¹ and X have the same meanings as defined in the general formulas (1) and (2).

In the above general formula (5), e is an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms which may have a substituent, and a carbon which may have a substituent. A dialkylamino group containing an alkyl chain of the number 1 to 3, a halogen atom or a hydrogen atom, i is 1 to 8
Indicates an integer. However, when i is 2 or more, a plurality of e may be the same or different and may form a ring with each other.

In the general formula (5), R ¹ ,
V, a, b, m and n have the same meanings as defined in the general formulas (1) and (4).

In the general formula (6), c and d
Are each an alkyl group having 1 to 5 carbon atoms which may contain a substituent, an alkoxy group having 1 to 3 carbon atoms which may contain a substituent, and a dialkyl containing an alkyl chain having 1 to 3 carbon atoms which may contain a substituent. It represents an amino group, a halogen atom or a hydrogen atom, and k and l represent an integer of 1 to 4. Where k
And when l is 2 or more, a plurality of corresponding c and d may be the same or different, and may form a ring with each other.

In the general formula (6), T is a group of atoms necessary for forming a ring, and includes an alkylene chain which may have a substituent, an unsaturated alkylene chain which may have a substituent, and a substituent. Represents an alkylene chain or an unsaturated alkylene chain containing a hetero atom which may be substituted or a hetero atom, which may contain a substituent. Specific examples thereof include methylene chains, alkylene chains such as ethylene chains and dimethylmethylene chains, unsaturated alkylene chains such as vinylene chains and propenylene chains, alkylene chains containing heteroatoms such as oxymethylene chains, and heterocycles such as thiovinylene chains. Examples thereof include an unsaturated alkylene chain containing an atom, a carbonyl group, SO ₂ , and a nitrogen atom having a substituent such as an oxygen atom, a sulfur atom, a selenium atom, and an alkyl group, and a hetero atom such as a silicon atom.

In the general formula (6), R ¹ ,
V, a, b, m and n have the same meanings as defined in the general formulas (1) and (4).

In the above general formulas (4), (5) and (6), specific examples of a, b, c, d, e and f include alkyl groups having 1 to 5 carbon atoms which may contain a substituent. Then, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, 1,1,1-trifluoroethyl,
For alkoxy groups having 1 to 3 carbon atoms such as fluoromethyl and 1-methoxyethyl, methoxy, ethoxy, n-
Examples of the dialkylamino group having an alkyl chain having 1 to 3 carbon atoms such as propoxy and isopropoxy include dimethylamino, diethylamino and diisopropylamino, and examples of the halogen atom include fluorine atom, chlorine atom and bromine atom.

In the above general formulas (4), (5) and (6), specific examples of V include alkylene chains such as methylene chains, ethylene chains, propylene chains and dimethylmethylene chains, vinylene chains and propenylene. Unsaturated alkylene chains such as chains, alkylene chains containing heteroatoms such as oxymethylene chains, unsaturated alkylene chains containing heteroatoms such as thiovinylene chains, carbonyl groups, S
Examples thereof include O ₂ , and a nitrogen atom having a substituent such as an oxygen atom, a sulfur atom, a selenium atom, and an alkyl group, and a hetero atom such as a silicon atom. Examples of the substituent which the nitrogen atom has include an alkyl group such as a methyl group and an ethyl group, and an aryl group such as a phenyl group, and the substituent which the silicon atom has include an alkyl group such as a methyl group and methoxy. And alkoxy groups such as ethoxy group, aryl groups such as phenyl group, and halogen atoms such as chlorine atom.

By having the structure represented by the general formula (4), (5) or (6), an enamine compound which is an organic photoconductive material having a high charge mobility can be obtained at a low cost.

The enamine compounds represented by the general formulas (2) to (6) are compounds contained in the enamine compound represented by the general formula (1) as described above. Specific examples of these enamine compounds include the compounds shown in Tables 1 to 24, but the enamine compounds of the present invention are not limited thereto.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

[0082]

[Table 9]

[0083]

[Table 10]

[0084]

[Table 11]

[0085]

[Table 12]

[0086]

[Table 13]

[0087]

[Table 14]

[0088]

[Table 15]

[0089]

[Table 16]

[0090]

[Table 17]

[0091]

[Table 18]

[0092]

[Table 19]

[0093]

[Table 20]

[0094]

[Table 21]

[0095]

[Table 22]

[0096]

[Table 23]

[0097]

[Table 24]

The enamine compound of the present invention can be easily produced at low cost by a conventionally known method, for example, as follows.

For example, the enamine compound represented by the general formula (3) of the present invention includes a cyclic aldehyde compound or a cyclic ketone compound represented by the following general formula (7) and a cyclic amine represented by the following general formula (8). The compound can be synthesized by subjecting it to a dehydration condensation reaction.

[0100]

[Chemical 19]

[0101]

[Chemical 20]

(In the general formulas (7) and (8), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , Y and Z are as defined in the general formulas (1) and (3). Synonymous.)

This dehydration condensation reaction is carried out, for example, as follows. A cyclic aldehyde compound or cyclic ketone compound represented by the general formula (7) and an equimolar amount of the cyclic amine compound represented by the general formula (8) are mixed with a non-polar solvent, alcohols, ethers and ketones. To prepare a solution. Specific examples of the solvent used include toluene, xylene, chlorobenzene, butanol, diethylene glycol dimethyl ether and methyl isobutyl ketone. An acid catalyst such as p-toluenesulfonic acid, camphorsulfonic acid and pyridinium-p-toluenesulfonic acid is added to the prepared solution, and the mixture is heated and reacted. The amount of the acid catalyst to be added is 1/10 to 1/1000 molar equivalent, preferably 1 / 25-1 / 500 molar equivalent to the cyclic aldehyde compound or cyclic ketone compound, and is 1/5.
The optimum range is 0 to 1/200 molar equivalent. Since water is by-produced during the reaction and hinders the reaction, the generated water is azeotropically distilled with a solvent and removed from the system. Thereby, the enamine compound represented by the general formula (3) can be produced in high yield.

Since the enamine compounds represented by the above general formulas (1) to (6) have a cyclic enamine structure, they have high charge mobility, high sensitivity and sufficient photoresponsiveness. But maintained. Therefore, by using an enamine compound having such characteristics as an organic photoconductive material for an electrophotographic photoreceptor, a sensor material, an EL element, an electrostatic recording element, etc., it is possible to provide a device having excellent responsiveness. it can.

Among the above enamine compounds, Ar ¹ and Ar ² are preferably a phenyl group or a p-tolyl group, and Z is a methylene chain, an oxygen atom or a sulfur, among the above-mentioned enamine compounds. A hetero atom containing a nitrogen atom having an atom or a methyl group, W and a nitrogen atom, Ar ⁵ , X and a nitrogen atom, or Ar ³ , Y, Ar ⁴ and a nitrogen atom together forms a carbazole ring, a phenothiazine ring, Examples thereof include a phenoxazine ring, an indole ring, a benzimidazole ring or a 2-phenylimidazole ring, and ^one in which R ¹ is a hydrogen atom.

The electrophotographic photosensitive member according to the present invention uses the enamine compounds represented by the general formulas (1) to (6) as a charge transporting substance, and has various embodiments.
Hereinafter, a detailed description will be given with reference to the drawings.

FIG. 1 is a sectional view schematically showing an example of an electrophotographic photosensitive member having a laminated photosensitive layer having a charge transport layer 6 on a charge generating layer 5. On the conductive support 1, as the photosensitive layer 4, the charge generation layer 5 having the charge generating substance 2 as the main component dispersed in the binder resin, and the charge having the charge transporting substance 3 as the main component dispersed in the binder resin. It is a multi-layer type photoreceptor that is formed by stacking the transport layer 6 and the transport layer 6. A charge transport layer 6 is formed on the surface of the charge generation layer 5, and the charge transport layer 6 contains the above-mentioned enamine compound as the charge transport substance 3.

FIG. 2 is a sectional view showing an example in which the electrophotographic photosensitive member of FIG. 1 has the intermediate layer 8. Conductive support 1
And the same photosensitive layer 4 as that shown in FIG. 1 with the intermediate layer 8 provided therebetween.

FIG. 3 is a sectional view schematically showing an example having an intermediate layer 8 in an electrophotographic photosensitive member having a single-layer type photosensitive layer having a charge generating substance 2 and a charge transporting substance 3 in the same layer. An intermediate layer 8 is provided on the conductive support 1, and a single layer type photosensitive layer 7 having a single layer in which a charge generating substance 2 and a charge transporting substance 3 are dispersed in a binder resin is provided as a dispersion type photosensitive layer 7. The constitution of the body is shown.

The electrophotographic photosensitive member according to the embodiment of the present invention can have various layer structures, with the typical structures shown in FIGS.

As the conductive support 1, aluminum,
Aluminum foil, metal drums and sheets such as copper, zinc, stainless steel and titanium, polymeric materials such as polyethylene terephthalate, nylon and polystyrene, hard paper and glass are subjected to metal foil lamination and metal deposition treatment, and conductive. Drums, sheets and seamless belts on which a layer of a conductive polymer, a conductive compound such as tin oxide and indium oxide is vapor-deposited or applied.

The surface of the conductive support 1 may be optionally subjected to anodic oxide film treatment, surface treatment with chemicals or hot water, coloring treatment, and the surface of the conductive support within a range not affecting the image quality. Random reflection processing such as roughening may be performed to prevent image defects due to interference of laser light having a regulated wavelength. This is because in an electrophotographic process using a laser as an exposure light source, the incident laser light and the light reflected in the electrophotographic photosensitive member interfere with each other, and the interference fringes appear on the image to cause an image defect. .

The intermediate layer 8 prevents image defects in the reversal development process, covers defects on the surface of the conductive support, improves chargeability, improves adhesiveness of the photosensitive layer, and improves coatability of the photosensitive layer. For the purpose of, it is provided between the conductive support 1 and the photosensitive layer 4 or 7. In particular, when an image is formed using the reversal development process, a toner image is formed on the portion of the exposed portion where the surface charge has decreased, so if the surface charge decreases due to factors other than exposure, the toner will adhere to the white background. Image fogging such as black spots occurs, and the image quality is significantly deteriorated. That is, the conductive support 1 and the photosensitive layer 4 or 7
Due to the decrease in the charging property in a minute area due to the defect of (1), it becomes a remarkable image defect such as image fog called minute black spot (black spot) where toner adheres to a white background. Prevent by layer 8.

As the material of the intermediate layer 8, various resin materials,
A resin material containing metal particles and metal oxide particles is used. Specific examples of the metal oxide particles include titanium oxide, aluminum oxide, aluminum hydroxide and tin oxide. Materials used when forming the intermediate layer 8 with a single resin layer include polyethylene resin, polypropylene resin, polystyrene resin,
Two or more of resin materials such as acrylic resin, vinyl chloride resin, vinyl acetate resin, polyurethane resin, epoxy resin, polyester resin, melamine resin, silicone resin, polyvinyl butyral resin, and polyamide resin, and monomers constituting these resins Copolymer resins containing, casein, gelatin, polyvinyl alcohol, and ethyl cellulose are known. Among these, a polyamide resin is particularly preferable, and an alcohol-soluble nylon resin can be used as a more preferable polyamide resin. For example 6-nylon, 66-nylon, 610-nylon, 11-nylon and 12-
A so-called copolymerized nylon obtained by copolymerizing nylon or the like, and a chemically modified type of nylon such as N-alkoxymethyl modified nylon and N-alkoxyethyl modified nylon are preferable.

The intermediate layer 8 contains a metal oxide such as titanium oxide to adjust the volume resistance value in the intermediate layer 8 to prevent injection of charges from the conductive support 1 and under various environments. In some cases, the electrical characteristics of the photoconductor may be maintained. In this case, a metal oxide such as titanium oxide can be dispersed in a solution prepared by dissolving the above resin in a solvent to prepare a coating liquid for the intermediate layer. Water and various organic solvents are used as the solvent. In particular, water, methanol, ethanol and butanol as a single solvent, as well as water and alcohols, 2
Preference is given to alcohols of at least one kind, alcohols such as acetone and dioxolane, and mixed solvents of chlorine-based solvents such as dichloroethane, chloroform and trichloroethane and alcohols.

As a method for dispersing the coating liquid for the intermediate layer, a general method such as a ball mill, a sand mill, an attritor, a vibration mill and an ultrasonic disperser can be applied. The total content A of the resin and the metal oxide in the coating solution for the intermediate layer is A relative to the content B of the solvent used in the coating solution for the intermediate layer.
It is preferable that / B has a weight ratio of 3/97 to 20/80. The resin / metal oxide weight ratio is 90/10 to 1 /
It is preferably 99, more preferably 70/30 to 5/95.

The intermediate layer 8 can be formed by applying the intermediate layer coating solution thus prepared by dispersion onto the conductive support 1. Examples of the coating method include spraying method, bar coating method, roll coating method, blade method, ring method and dipping method. From these coating methods, the most suitable method can be selected in consideration of the physical properties and productivity of the coating. In the dip coating method, the intermediate layer 8 is formed by immersing the conductive support 1 in a coating tank filled with the coating liquid for the intermediate layer, and then pulling the conductive support 1 at a constant rate or a rate that changes sequentially. As described above, the dip coating method is relatively simple and excellent in productivity and cost. Therefore, the dip coating method is often used for manufacturing an electrophotographic photoreceptor. An apparatus used for the dip coating method may be provided with a coating liquid dispersion device typified by an ultrasonic wave generator in order to stabilize the dispersibility of the coating liquid.

The thickness of the intermediate layer 8 is preferably 0.01 μm.
The range is from m to 20 μm, and more preferably from 0.05 μm to 10 μm. The thickness of the intermediate layer 8 is 0.01
If it is thinner than μm, it will not function as the intermediate layer 8 substantially. That is, the defects of the conductive support 1 cannot be covered to obtain a uniform surface property, the injection of charges from the conductive support 1 cannot be prevented, and the chargeability decreases. In addition, it is not preferable to make the thickness of the intermediate layer 8 thicker than 20 μm, because when the intermediate layer 8 is applied by dip coating, the production of the photoreceptor becomes difficult and the sensitivity of the photoreceptor is lowered.

As the substance effective as the charge generating substance 2, azo pigments such as monoazo, bisazo and trisazo pigments, indigo pigments such as indigo and thioindigo, perylene imides such as perylene imide and perylene anhydride, anthraquinone and Examples include polycyclic quinone pigments such as pyrenequinone, phthalocyanine compounds such as metal phthalocyanines and non-metal phthalocyanines, squarylium dyes, pyrylium salts and thiopyrylium salts, triphenylmethane dyes, and inorganic materials such as selenium and amorphous silicon. To be These charge generating substances may be used alone or in combination of two or more kinds.

The charge-generating substance 2 is a triphenylmethane dye typified by methyl violet, crystal violet, night blue and Victoria blue, erythrosine, rhodamine B, rhodamine 3R, acridine orange and flapeosin. Dyes, thiazine dyes typified by methylene blue and methylene green, oxazine dyes typified by capri blue and meldra blue, cyanine dyes, styryl dyes, pyrylium salt dyes and thiopyrylium salt dyes May be combined.

As the method for forming the charge generating layer 5, there are a method of forming the charge generating substance 2 by vacuum vapor deposition, and a method of mixing and dispersing it in an organic solvent in which a binder resin is dissolved to form a film. . Among these, a method in which the charge generating substance 2 is dispersed in a binder resin solution by a known method and then applied is preferable.

As the binder resin of the charge generating layer 5, polyester resin, polystyrene resin, polyurethane resin, phenol resin, alkyd resin, melamine resin,
Resins such as epoxy resin, silicone resin, acrylic resin, methacrylic resin, polycarbonate resin, polyarylate resin, phenoxy resin, polyvinyl butyral resin and polyvinyl formal resin, and resins containing two or more of repeating units of these resins. A polymer resin is used. Examples of the copolymer resin include vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin and acrylonitrile-styrene copolymer resin. . The binder resin is not limited to these, and all commonly used resins can be used alone or in combination of two or more.

Solvents for dissolving these binder resins include halogenated hydrocarbons such as dichloromethane and dichloroethane, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran (TH
F) and ethers such as dioxane, cellosolves such as 1,2-dimethoxyethane, aromatic hydrocarbons such as benzene, toluene and xylene, aprotons such as N, N-dimethylformamide and N, N-dimethylacetamide. A polar solvent, a mixed solvent thereof, or the like can be used.

The compounding ratio of the charge generating substance 2 and the binder resin is preferably such that the ratio of the charge generating substance 2 is 10% by weight to 99% by weight. If the proportion of the charge generating substance 2 is less than this range, the sensitivity is lowered, and if it is more than the above range, not only the film strength of the charge generating layer 5 is lowered, but also the dispersibility is lowered and the coarse particles are increased, so that the image is increased. There are many defects, especially black spots.

Before the charge generating substance 2 is mixed and dispersed in the binder resin solution, the binder resin may be pulverized by a pulverizer in advance. Examples of the pulverizer used for the pulverization include a ball mill, a sand mill, an attritor, a vibration mill and an ultrasonic disperser. Appropriate conditions are selected as the dispersion conditions so that impurities are not mixed due to abrasion of the container and the dispersion medium used.

Examples of the coating method of the binder resin solution obtained by mixing and dispersing the charge generating substance 2 include spray method, bar coating method, roll coating method, blade method, ring method and dipping method. In particular, the dip coating method is relatively simple as described above and is excellent in productivity and cost. Therefore, the dip coating method is often used for forming the charge generation layer 5.

The thickness of the charge generation layer 5 is preferably 0.0.
The range is 5 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 1 μm or less.

The charge transport layer 6 is composed of the above-mentioned general formulas (1) to (1).
It is obtained by incorporating one or more kinds of the enamine compounds represented by (6) into the binder resin. As described above, the enamine compound has high charge mobility, high sensitivity, and good photoresponsiveness. Further, it exhibits sufficient photoresponsiveness even in a low temperature environment, and their characteristics do not change even after repeated use. Therefore, the enamine compound is used as the charge transport material 3
By using as a high charge potential and high sensitivity,
It is also possible to provide an electrophotographic photosensitive member which is excellent in durability and does not deteriorate in sensitivity even when used in a low temperature environment and in a high speed process.

The charge transport layer 6 includes the above general formulas (1) to (1).
In addition to the enamine compound represented by (6), other charge transport materials 3 may be mixed and used depending on the case. Examples of the other charge transport material 3 include a carbazole derivative, an oxazole derivative, an oxadiazole derivative, a thiazole derivative, a thiadiazole derivative, a triazole derivative, an imidazole derivative, an imidazolone derivative, an imidazolidine derivative, a bisimidazolidine derivative, a styryl compound, a hydrazone compound, Polycyclic aromatic compound, indole derivative, pyrazoline derivative, oxazolone derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, triarylamine derivative, triarylmethane derivative, phenylenediamine derivative, stilbene derivative And derivatives of benzidine.
Also included are polymers having groups consisting of these compounds in the main chain or side chains, such as poly-N-vinylcarbazole, poly-1-vinylpyrene and poly-9-vinylanthracene, and polysilane.

The binder resin for the charge transport layer 6 is selected to be compatible with the charge transport material 3. For example, vinyl polymers such as polymethylmethacrylate, polystyrene and polyvinyl chloride and copolymers thereof, as well as polycarbonate resin, polyester resin, polyester carbonate resin, polysulfone resin, phenoxy resin, epoxy resin, silicone resin, polyarylate resin, polyamide Resins such as resins, polyurethane resins, polyacrylamide resins and phenol resins are mentioned. These may be used alone or in combination of two or more, or may be a partially crosslinked thermosetting resin. In particular, resins such as polystyrene, polycarbonate, polyarylate and polyphenylene oxide have a volume resistance value of 10 ¹³ Ω or more, and are excellent in film formability and potential characteristics.

The addition ratio D / C of the binder resin (C) and the enamine compound (D) to the charge transport layer 6 is generally about 10/12 by weight. Since the above-mentioned enamine compound has a high mobility, the weight ratio D / C of the enamine compound / binder resin is set to 10/12 to 10/30 while maintaining high sensitivity to increase the binder resin content. be able to. By thus increasing the content of the binder resin, the printing durability of the charge transport layer 6 is improved, and the durability of the electrophotographic photosensitive member according to the present embodiment can be improved. The weight ratio D / C is 10/3
When it is smaller than 0, that is, when the ratio of the binder resin is high, the viscosity of the coating liquid increases, so that the coating speed is lowered when the photosensitive drum is manufactured by the dip coating method, and the productivity is significantly deteriorated. On the other hand, the weight ratio D / C is 10/1
If it is larger than 2, that is, if the ratio of the binder resin becomes low, the viscosity of the coating liquid decreases, so that an appropriate film thickness can be secured even if the coating speed is adjusted when the photosensitive drum is manufactured by the dip coating method. The problem arises that it becomes difficult. Even if the film thickness can be ensured, the wear resistance cannot be ensured because the degree of increase in the amount of wear is greater than when the ratio of the binder resin is high.

If necessary, a conventionally known plasticizer and a silicone-based leveling agent may be added to the charge transport layer 6 to impart processability and flexibility to the photosensitive layer 4 and improve surface smoothness. You can also Examples of the plasticizer include dibasic acid ester, fatty acid ester, phosphoric acid ester, phthalic acid ester, chlorinated paraffin and epoxy type plasticizer.

Further, fine particles of an inorganic or organic compound may be added to the charge transport layer 6 so as to increase mechanical strength and electric characteristics.

Further, the charge transport layer 6 may contain various additives such as an antioxidant and a sensitizer, if necessary. In particular, hindered phenol derivatives and hindered amine derivatives are suitable as antioxidants. The hindered phenol derivative is preferably contained in the charge transport substance 3 in an amount of 0.1% by weight or more and 50% by weight or less, and the hindered amine derivative is contained in the charge transport substance 3 in an amount of 0.1% by weight or more and 50% by weight or less. It is preferably included. As a result, the potential characteristics are improved and the stability of the coating liquid is also increased.

The charge transport layer 6 is formed in the same manner as the above-mentioned intermediate layer 8 and charge generation layer 5 by using, for example, a suitable organic solvent, a spray method, a bar coating method, a roll coating method,
It can be carried out by a blade method, a ring method and a dipping method. In particular, the dip coating method is widely used because it is excellent in various points as described above. As the coating solvent, aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene, halogenated hydrocarbons such as dichloromethane and dichloroethane, THF, dioxane,
A single solvent such as dimethoxymethyl ether and N, N-dimethylformamide or a mixed solvent of two or more kinds is used, and if necessary, a solvent such as alcohols, acetonitrile and methyl ethyl ketone can be further added and used.

The thickness of the charge transport layer 6 is preferably 5 to 50 μm, more preferably 10 to 40 μm.

In the case of a single layer type photoreceptor, the charge generating substance 2, the charge transporting substance 3 and the binder resin are dissolved and mixed and dispersed in the above-mentioned suitable solvent to prepare a coating liquid, and the coating liquid is prepared. Is applied by the dip coating method or the like to form a single-layer photosensitive layer 7. The addition ratio of the binder resin and the enamine compound to the photosensitive layer 7 and the film thickness of the photosensitive layer 7 are the same as in the case of the above-mentioned laminated type photoreceptor.

The photosensitive layer 4 or 7 may further contain one or more kinds of electron accepting substances or dyes to improve the sensitivity so as to suppress an increase in residual potential and fatigue during repeated use. Examples of the electron acceptor include acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride and 4-chloronaphthalic anhydride, cyano compounds such as tetracyanoethylene and terephthalmalondinitrile, 4-nitrobenzaldehyde and the like. Aldehydes, anthraquinones such as anthraquinone and 1-nitroanthraquinone, polycyclic or heterocyclic nitro compounds such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitrofluorenone, diphenoquinone compounds, and Polymerized materials of these electron-withdrawing materials can be used. As the dye, for example, a xanthene dye, a thiazine dye, a triphenylmethane dye, a quinoline dye, and an organic photoconductive compound such as copper phthalocyanine can be used as an optical sensitizer.

By providing a protective layer on the surface of the photosensitive layer 4 or 7, it is possible to improve the abrasion property of the photosensitive layer 4 or 7 and prevent chemical adverse effects due to ozone and nitrogen oxides.

If necessary, various kinds of additives such as antioxidants, ultraviolet absorbers and sensitizers may be added to the respective layers of the photoreceptor. In particular, examples of the antioxidant include phenol compounds, hydroquinone compounds, tocopherol compounds, amine compounds and the like. These antioxidants are contained in 0.1% by weight with respect to the charge transport material 3.
It is preferable that the content is not less than 50% by weight. As a result, the potential characteristics are improved, the stability as a coating liquid is also increased, fatigue deterioration when the photoreceptor is repeatedly used can be reduced, and durability can be improved.

Next, an image forming apparatus equipped with the electrophotographic photosensitive member having the above-described structure will be described. The image forming apparatus according to the embodiment of the present invention is not limited to the contents described below.

FIG. 4 is a block diagram showing a schematic structure of an image forming apparatus equipped with an electrophotographic photosensitive member according to an embodiment of the present invention. Around the electrophotographic photosensitive member 11, a charger 32, a semiconductor laser 31, a developing device 33, a transfer charger 34, a fixing device 35, and a cleaner 36 are sequentially arranged.

The drum-shaped electrophotographic photosensitive member 11 is rotationally driven in the direction of arrow 41 at a predetermined peripheral speed by a driving means (not shown). During the rotation process, the photoconductor 11 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the contact type or non-contact type charger 32. Next, the laser beam from the semiconductor laser 31 is repeatedly scanned on the surface of the photoconductor 11 in its longitudinal direction (main scanning direction),
An electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 11. The formed electrostatic latent image is developed as a toner image by the developing device 33 provided on the downstream side in the rotation direction with respect to the image formation point of the semiconductor laser 31.

The transfer paper 5 is synchronized with the exposure of the photoreceptor 11.
1 is given from the direction of arrow 42 to the transfer charger 34 provided further downstream in the rotational direction of the developing device 33, and the transfer paper 5
The toner image is transferred to No. 1. The transfer paper 51 is conveyed to the fixing device 35 by the conveyance belt, and the toner image is transferred onto the transfer paper 51.
Is fixed in. The transfer paper 51 on which the image is formed in this manner is ejected. The toner remaining on the surface of the photoconductor 11 is cleaned by a cleaner 36 provided together with a charge eliminating lamp (not shown) on the downstream side of the transfer charger 34 in the rotational direction and the upstream side of the charger 32 in the rotational direction. Further, by rotating the photoconductor 11, the above-described rotation process is repeated to form an image.

By mounting the electrophotographic photosensitive member containing the above-mentioned enamine compound as a charge transporting substance, it has high sensitivity and excellent durability, and its electric characteristics are not deteriorated even when used in a low temperature environment and a high speed process. An image forming apparatus can be provided.

[0146]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Synthesis Example 1 Exemplified Compound No. Synthesis of 1 To 100 ml of toluene, 16.7 g of carbazole (1.0
21.9 g (1.05 equivalent) of a cyclic aldehyde compound represented by the following structural formula (9) and 0.23 g (0.01 equivalent) of DL-10-camphorsulfonic acid were added and heated to form a by-product. The reaction was carried out for 6 hours while azeotropically distilling water with toluene to remove it from the system. After completion of the reaction, the reaction mixture was concentrated to about 1/10 and gradually added dropwise to 100 ml of hexane which was vigorously stirred for crystallization. The generated crystals were filtered and washed, and the exemplified compound No. 1 shown in Table 1 was used.
28.9 g of the enamine compound of 1 was obtained as a pale yellow powder compound (yield 81%). LC of the obtained enamine compound
As a result of analysis by -MS (liquid chromatography-mass spectrometry), purity was 99.1%, (M + H) ⁺ = 358.6.
It was (Calcd = 357.15).

[0148]

[Chemical 21]

Synthesis Example 2 Exemplified Compound No. The synthetic phenothiazine of 121 and 11.0 g of a cyclic aldehyde compound represented by the following structural formula (10) were used as starting materials, and enamined as in Synthesis Example 1.
Exemplary compound No. 1 shown in FIG. 121 enamine compounds 3
2.0 g was obtained as a pale yellow powder compound (yield 82
%). As a result of analyzing the obtained enamine compound by LC-MS, the purity was 99.1% and (M + H) ⁺ = 392.6 (C
alcd = 391.10).

[0150]

[Chemical formula 22]

Example 1 After 1 part by weight of an azo compound represented by the following structural formula (11) was added to a resin solution in which 99 parts by weight of THF was dissolved 1 part by weight of a phenoxy resin (PKHH manufactured by Union Carbide Co.). , With paint shaker 2
After time-dispersion, a charge generation layer coating liquid was prepared. This charge generation layer coating liquid was applied onto a polyester film (film thickness 80 μm) vapor-deposited on aluminum so that the film thickness after drying was 0.3 μm by a baker applicator to form a charge generation layer.

[0152]

[Chemical formula 23]

Then, the exemplified compound No. 1 shown in Table 1 was used. 1
8 parts by weight of the enamine compound and 10 parts by weight of a polycarbonate resin (C-1400 manufactured by Teijin Chemicals Ltd.) were added to THF80.
A coating solution for a charge transport layer was prepared by dissolving it in parts by weight. This charge transport layer coating liquid on the charge generating layer previously formed,
A baker applicator was applied so that the film thickness after drying would be 10 μm to form a charge transport layer.

Thus, a laminated electrophotographic photosensitive member having the layer structure shown in FIG. 1 was produced.

(Examples 2 to 6) In Example 1, the exemplified compound No. 1 instead of the exemplary compound Nos. 1 to 24 shown in Tables 1 to 24. In the same manner as in Example 1 except that the enamine compounds of 24, 98, 121, 149 and 185 were used,
Five types of electrophotographic photoconductors were produced.

(Comparative Example 1) In Example 1, the exemplified compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the comparative compound A represented by the following structural formula (12) was used in place of 1.

[0157]

[Chemical formula 24]

(Evaluation 1) The ionization potentials of the electrophotographic photosensitive members produced in the above Examples 1 to 6 and Comparative Example 1 were measured using a surface analyzer (AC-1 manufactured by Riken Keiki Co., Ltd.). In addition, after depositing gold on the upper surface of these electrophotographic photosensitive members, Time-of-
Mobility was measured by the Flight method. Table 25 shows the evaluation results. The mobility shows a value when the electric field strength is 2.5 × 10 ⁵ V / cm.

[0159]

[Table 25]

From the results shown in Table 25, the enamine compounds of the examples are comparative compound A which is an enamine compound which has been conventionally used and TPD which is a typical charge transporting substance.
(Triphenylamine dimer; mobility = 1.2 x 10 ^-6 cm
² / V · sec) and the like, it has been found that the ionization potential is about the same, but the mobility is 2 to 4 orders of magnitude higher.

(Example 7) 9 parts by weight of dendritic titanium oxide (TTO-D-1 manufactured by Ishihara Sangyo Co., Ltd.) surface-treated with Al ₂ O ₃ and ZrO ₂ and a copolymerized nylon resin (Toray Industries, Inc.) CM8000) 9 parts by weight was added to a mixed solvent of 41 parts by weight of 1,3-dioxolane and 41 parts by weight of methanol and dispersed for 12 hours using a paint shaker to prepare a coating solution for the intermediate layer. The prepared coating solution for intermediate layer was applied onto an aluminum substrate with a baker applicator so that the film thickness after drying would be 1 μm to form an intermediate layer.

Then, 2 parts by weight of the azo compound represented by the following structural formula (13) was added to a resin solution prepared by dissolving 1 part by weight of polyvinyl butyral resin (BX-1 manufactured by Sekisui Chemical Co., Ltd.) in 97 parts by weight of THF. Then, the mixture was dispersed for 10 hours with a paint shaker to prepare a charge generation layer coating liquid. This charge generation layer coating solution was applied onto the intermediate layer previously formed so that the film thickness after drying was 0.3 μm using a baker applicator to form a charge generation layer.

[0163]

[Chemical 25]

Then, the exemplified compound No. 1 shown in Table 1 was used. 1
10 parts by weight of an enamine compound, 14 parts by weight of a polycarbonate resin (Z200 manufactured by Mitsubishi Gas Chemical Co., Inc.), 2,6-
Di-t-butyl-4-methylphenol (0.2 parts by weight) was dissolved in THF (80 parts by weight) to prepare a charge transport layer coating solution. The charge transport layer coating solution was applied onto the previously formed charge generating layer by a baker applicator so that the film thickness after drying was 18 μm to form a charge transport layer.

In this way, a laminated electrophotographic photosensitive member having the layer structure shown in FIG. 2 was produced.

(Examples 8 to 12) In Example 7, the exemplified compound No. 1 instead of the exemplary compound Nos. 1 to 24 shown in Tables 1 to 24. Five types of electrophotographic photosensitive members were produced in the same manner as in Example 7 except that the enamine compounds of 24, 98, 121, 149 and 185 were used.

(Comparative Example 2) In Example 7, the exemplified compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the comparative compound A represented by the structural formula (12) was used in place of 1.

(Comparative Example 3) In Example 7, the exemplified compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the comparative compound B represented by the following structural formula (14) was used in place of 1.

[0169]

[Chemical formula 26]

Example 13 An intermediate layer coating solution was prepared in the same manner as in Example 7, and this was applied onto an aluminum substrate so that the film thickness after drying would be 1 μm to form an intermediate layer.

Next, 1 part by weight of the azo compound represented by the structural formula (13), 12 parts by weight of a polycarbonate resin (Z-400 manufactured by Mitsubishi Gas Chemical Co., Inc.), and the exemplified compound No. 1 of 1
0 part by weight, 3,5-dimethyl-3 ', 5'-di-t-butyldiphenoquinone 5 parts by weight, 2,6-di-t-butyl-4-methylphenol 0.5 part by weight and THF65.
Parts by weight were dispersed with a ball mill for 12 hours to prepare a photosensitive layer coating liquid. After coating the prepared photosensitive layer coating liquid on the previously formed intermediate layer with a baker applicator, 110 ° C
And dried with hot air for 1 hour to form a photosensitive layer with a dry film thickness of 20 μm.

Thus, a single-layer type electrophotographic photosensitive member having the layer structure shown in FIG. 3 was produced.

(Example 14) In Example 7, except that an X type metal-free phthalocyanine was used in place of the azo compound represented by the structural formula (13) as the charge generating substance,
An electrophotographic photosensitive member was produced in the same manner as in Example 7.

(Examples 15 to 19) In Example 7,
Instead of the azo compound represented by the structural formula (13) as the charge generating substance, an X-type metal-free phthalocyanine was used, and the compound No. 1 instead of 1
Exemplary compound No. 24 shown in FIG. 24, 98, 121, 1
Five types of electrophotographic photosensitive members were produced in the same manner as in Example 7 except that the enamine compounds of 49 and 185 were used.

(Comparative Examples 4 and 5) In Example 7,
Instead of the azo compound represented by the structural formula (13) as the charge generating substance, an X-type metal-free phthalocyanine was used, and the compound No. Two types of electrophotographic photosensitizers were prepared in the same manner as in Example 7, except that the comparative compound A represented by the structural formula (12) and the comparative compound B represented by the structural formula (14) were used in place of 1. The body was made.

(Evaluation 2) The electrophotographic photosensitive members produced in Examples 7 to 19 and Comparative Examples 2 to 5 described above were evaluated using an electrostatic copying paper test apparatus (EPA-8200 manufactured by Kawaguchi Denki KK). The measurement is at room temperature / normal humidity environment (under N / N environment) of 22 ° C./65% RH and at low temperature of 5 ° C./20% RH /
The test was performed in each of the low humidity environment (L / L environment). As an evaluation of the initial characteristics, the sensitivity (E _1/2 [μJ / c) which is the exposure amount required to halve the potential by exposure is used.
m ² ]), the charging potential (V ₀ [V]) when -5 kV is applied to the photoconductor, and the residual potential (V _r after 10 seconds of exposure).
[V]) was measured. For the exposure, white light of 1 μW / cm ² was used in the case of a photoreceptor using the azo compound represented by the structural formula (13) as a charge generating substance, and in the case of a photoreceptor using X-type metal-free phthalocyanine. Light having a wavelength of 780 nm and 1 μW / cm ² dispersed by a monochromator was used. Further, as evaluation of the repeating characteristics, the sensitivity (E _1/2 ), the charging potential (V ₀ ) and the residual potential (V _r ) after repeating charging and exposure 5000 times were measured. Table 26 shows the evaluation results.

[0177]

[Table 26]

Example 20 9 parts by weight of dendritic titanium oxide (TTO-D-1 manufactured by Ishihara Sangyo Co., Ltd.) surface-treated with Al ₂ O ₃ and ZrO ₂ and a copolymerized nylon resin as a binder resin (Toray's CM8000) 9 parts by weight, 1,3-dioxolane 41 parts by weight and methanol 41
After adding to a mixed solvent with 1 part by weight, it was dispersed for 8 hours with a paint shaker to prepare an intermediate layer coating solution. The coating solution for the prepared intermediate layer was filled in a coating tank, and an aluminum-made cylindrical support having a diameter of 40 mm and a total length of 340 mm was used as a conductive support, and an intermediate layer having a thickness of 1.0 μm was made conductive by a dip coating method. Formed on a support.

Then, as oxotitanyl phthalocyanine which is a charge generating substance, at least 2 at a Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction.
2 parts by weight of an oxotitanyl phthalocyanine pigment having a clear diffraction peak at 7.3 °, 1 part by weight of a polyvinyl butyral resin (Eslek BM-S manufactured by Sekisui Chemical Co., Ltd.), and 97 parts by weight of methyl ethyl ketone were mixed to prepare a paint shaker. Was dispersed to prepare a charge generation layer coating solution.
The prepared charge generation coating liquid was applied in the same manner as the above-mentioned intermediate layer to form a 0.4 μm-thick charge generation layer on the previously formed intermediate layer.

Then, the exemplified compound No. 1 shown in Table 3 was used. Two
10 parts by weight of the enamine compound of No. 4, 20 parts by weight of a polycarbonate resin (Iupilon Z200 manufactured by Mitsubishi Engineering Plastics), and 2,6-di-t-butyl-4.
1 part by weight of methylphenol and 1 part by weight of dimethylpolysiloxane (KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.) were added to TH.
Dissolved in F to prepare a charge transport layer coating solution having a solid content of 23% by weight. The prepared charge transport layer coating solution is applied onto the charge generating layer previously formed by a dip coating method, and then the temperature is set to 110 ° C.
And dried for 1 hour to form a charge transport layer having a thickness of 23 μm.
An electrophotographic photoreceptor was produced.

(Examples 21 and 22) In Example 20, the exemplified compound No. 24 in place of Example Compound No. 24 shown in Tables 1 to 24. Two types of electrophotographic photosensitive members were produced in the same manner as in Example 20 except that the enamine compounds of 121 and 226 were used.

(Comparative Example 6) In Example 20, the exemplified compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 20 except that the comparative compound A represented by the structural formula (12) was used in place of 24.

(Example 23) An electrophotographic photosensitive member was prepared in the same manner as in Example 20, except that the polycarbonate resin in the coating liquid for charge transport layer was changed to 25 parts by weight.

(Examples 24 and 25) In Example 20, 2 parts of the polycarbonate resin of the charge transport layer coating liquid was used.
5 parts by weight, and exemplified compound No. Table 1 instead of 24
Exemplary compound No. 24 shown in FIG. Two types of electrophotographic photosensitive members were produced in the same manner as in Example 20 except that the enamine compounds of 121 and 226 were used.

(Evaluation 3) The electrophotographic photoconductors produced in the above Examples 20 to 25 and Comparative Example 6 were mounted on a digital copying machine (AR-C150 manufactured by Sharp Corp.) having a process speed of 117 mm / sec. As a durability test,
The initial film thickness and the film thickness of 40,000 sheets after the end of actual copying were measured, and the film reduction amount Δd, which was the difference between them, was obtained. Also, as a stability test of electrical characteristics, 22 ° C / 65% RH
Charge potential V ₀ and surface potential V _L after laser exposure under N / N environment, and L / L of 5 ° C./20% RH
The surface potential under the environment was measured, and the potential fluctuation ΔV _L , which is the difference between this and the surface potential V _L under the N / N environment, was determined. The negative sign shown in the column of ΔV _L represents a decrease in the absolute value of the potential. Table 27 shows the evaluation results.

[0186]

[Table 27]

From the results shown in Tables 26 and 27, it was found that the electrophotographic photoreceptors of Examples had higher sensitivities because the enamine compounds of Examples had higher mobilities than those of Comparative Examples. Further, it was found that various electric characteristics are good even under the L / L environment, and even if the ratio of the binder resin to the enamine compound which is the charge transport material is increased, the electric characteristics are good.

From the above results, it was found that the use of the enamine compound of the present invention can provide an electrophotographic photosensitive member having high sensitivity and high durability.

[0189]

As described above, according to the present invention, an enamine compound which is an organic photoconductive material having a high charge mobility can be obtained by having a specific structure, particularly a cyclic enamine structure.

Further, according to the present invention, by containing the enamine compound having the above-mentioned specific structure in the photosensitive layer as a charge transporting substance, it has high sensitivity and excellent durability and is used in a low temperature environment and a high speed process. Moreover, it is possible to obtain an electrophotographic photosensitive member and an image forming apparatus whose electric characteristics are not deteriorated.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing an example of an electrophotographic photoreceptor having a laminated photosensitive layer having a charge transport layer 6 on a charge generation layer 5.

2 is a cross-sectional view showing an example having an intermediate layer 8 in the electrophotographic photosensitive member of FIG.

FIG. 3 is a cross-sectional view schematically showing an example in which an intermediate layer 8 is provided in an electrophotographic photoreceptor having a single-layer type photosensitive layer having a charge generating substance 2 and a charge transporting substance 3 in the same layer.

FIG. 4 is a configuration diagram showing a schematic configuration of an image forming apparatus including an electrophotographic photosensitive member according to an embodiment of the present invention.

[Explanation of symbols]

1 Conductive support 2 Charge generation material 3 Charge transport material 4,7 Photosensitive layer 5 Charge generation layer 6 Charge transport layer 8 Middle class 11 Electrophotographic photoreceptor 31 Semiconductor laser 32 charger 33 Developer 34 Transfer charger 35 fixer 36 cleaner 51 transfer paper

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 417/06 C07D 417/06 G03G 5/06 313 G03G 5/06 313 315 315A F term (reference) 2H068 AA20 BA13 BA16 4C036 AA02 AA11 AA17 4C063 AA01 BB03 CC16 CC79 CC95 DD06 DD08 DD64 EE10 4C204 BB09 CB25 DB01 EB01 FB04 GB01

Claims (10)

[Claims] 1. An enamine compound represented by the following general formula (1): [Chemical 1] (In the formula, Ar ¹ and Ar ² each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Z represents Ar ¹ , a carbon atom and Ar ² to form a ring. And W represents an atomic group necessary for forming a ring together with a nitrogen atom, and R ¹ represents a hydrogen atom or an alkyl group which may have a substituent. 2. The enamine compound according to claim 1, wherein the enamine compound represented by the general formula (1) is represented by the following general formula (2). [Chemical 2] (In the formula, Ar ⁵ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. X represents an atomic group necessary for forming a ring together with Ar ⁵ and a nitrogen atom. Ar ¹ , Ar ² , R ¹ and Z are represented by the general formula (1)
Is synonymous with that defined in. ) 3. The enamine compound according to claim 1, wherein the enamine compound represented by the general formula (1) is represented by the following general formula (3). [Chemical 3] (In the formula, Ar ³ and Ar ⁴ each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Y represents a ring together with Ar ³ , a nitrogen atom and Ar ⁴ ; Represents the necessary atomic group. Ar ¹ , Ar ² , R ¹ and Z have the same meanings as defined in the general formula (1).) 4. The enamine compound according to claim 2, wherein the enamine compound represented by the general formula (2) is represented by the following general formula (4). [Chemical 4] (In the formula, a, b and f are each an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms which may have a substituent, and a carbon number which may have a substituent. A dialkylamino group containing 1 to 3 alkyl chains, a halogen atom or a hydrogen atom, and j, m and n are 1 to 4
Indicates an integer. However, when j, m and n are 2 or more, a plurality of corresponding a, b and f may be the same or different and may form a ring with each other. V is a group of atoms necessary for forming a ring, which may contain an alkylene chain which may have a substituent, an unsaturated alkylene chain which may have a substituent, a hetero atom which may have a substituent, or a substituent. Represents an alkylene chain containing a hetero atom or an unsaturated alkylene chain. R ¹ and X have the same meanings as defined in the general formulas (1) and (2). ) 5. The enamine compound according to claim 2, wherein the enamine compound represented by the general formula (2) is represented by the following general formula (5). [Chemical 5] (In the formula, a, b and e are each an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms which may have a substituent, and a carbon number which may have a substituent. A dialkylamino group containing an alkyl chain of 1 to 3, a halogen atom or a hydrogen atom is shown, i is an integer of 1 to 8, m and n are integers of 1 to 4, provided that i, m and n.
When is 2 or more, a plurality of corresponding a, b and e may be the same or different and may form a ring with each other. V is a group of atoms necessary for forming a ring, which may contain an alkylene chain which may have a substituent, an unsaturated alkylene chain which may have a substituent, a hetero atom which may have a substituent, or a substituent. Represents an alkylene chain containing a hetero atom or an unsaturated alkylene chain. R ¹ has the same meaning as defined in the general formula (1). ) 6. An enamined compound represented by the general formula (3)
The compound is represented by the following general formula (6).
The enamine compound according to claim 3. [Chemical 6] (In the formula, each of a, b, c and d may include a substituent.
Good C1-5 alkyl group, may contain a substituent
Charcoal having 1 to 3 carbon atoms and optionally containing a substituent
A dialkylamino group containing an alkyl chain having a prime number of 1 to 3,
Rogen atom or hydrogen atom, k, l, m and n
Represents an integer of 1 to 4. Where k, l, m and n are
When two or more, the corresponding plural a, b, c and d are the same.
They may be one or different and may form a ring with each other. V
And T are atomic groups necessary for forming a ring,
An alkylene chain that may contain a substituent, or a substituent
Good unsaturated alkylene chain, optionally substituted hetero
Containing an atom, or heteroatom, which may contain a substituent
An alkylene chain or an unsaturated alkylene chain is shown. R ¹
Has the same meaning as defined in the general formula (1).
It ) 7. An electrophotographic photoreceptor comprising the enamine compound according to claim 1 as a charge transporting substance in a photosensitive layer provided on a conductive support. 8. The photosensitive layer has a laminated structure having at least a charge generating layer containing a charge generating substance and a charge transporting layer containing the charge transporting substance. Electrophotographic photoreceptor. 9. The electrophotographic photosensitive member according to claim 7, further comprising an intermediate layer provided between the conductive support and the photosensitive layer. 10. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 7.