JPH0836269A - Electrophotographic photoreceptor - Google Patents

Abstract

(57) [Summary] [Structure] In an electrophotographic photoreceptor, a photosensitive layer formed on a conductive support has the following structural formula: (Here, Ar is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent or a heterocyclic-substituted alkyl group, and n is 2, 3, or 4) is contained as a carrier transfer substance. [Effect] The electrophotographic photoreceptor has excellent sensitivity and durability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more particularly to an electrophotographic photosensitive member in which a specific enamine derivative is contained in a photosensitive layer formed on a conductive support. is there.

[0002]

2. Description of the Related Art Generally, there are various methods in an electrophotographic process, and as typical examples thereof, a direct method and a latent image transfer method are known. In the electrophotographic photosensitive member used in these electrophotographic processes, the basic properties required for the photoconductive material constituting the photoconductive layer are: 1) High charging potential due to corona discharge in the dark. 2) The obtained electric charge due to corona discharge is less attenuated in a dark place. 3) Charge should be rapidly dissipated by light irradiation. 4) The residual charge after light irradiation is small. 5) The residual potential does not increase and the initial potential decreases with repeated use. 6) Little change in electrophotographic characteristics due to temperature and humidity. And so on.

As such materials, there have hitherto been used inorganic photoconductive materials such as zinc oxide (Japanese Patent Publication No. 57-19780), cadmium sulfide (Japanese Patent Publication No. 58-46018), and amorphous selenium alloys. It has been used, but in recent years various problems have been pointed out. That is, a zinc oxide-based material requires a sensitizing effect by the addition of a sensitizer, but since these sensitizers cause charge deterioration due to corona discharge and photobleaching due to exposure, a stable image can be obtained for a long time. Can't give. Cadmium sulfide-based materials cannot provide stable sensitivity under humid conditions. For selenium-based materials, the temperature,
For example, crystallization easily progresses due to external factors such as humidity, chargeability is reduced, white spots appear on images, manufacturing conditions are difficult, and toxicity is high.

Therefore, from a future perspective, research on electrophotographic photoreceptors made of organic materials rather than inorganic materials, which have problems of resource depletion, toxicity concerns, and environmental problems, has been actively conducted. As a result, electrophotographic photoconductors using various organic compounds have been studied. In particular, research and development in the past few years have been aimed at positively introducing the concern of the function-separated type photoreceptor, and in particular, a carrier generation layer and a hole transfer carrier transfer layer are formed on a conductive substrate. The method of stacking layers in order and negatively charging the surface of the carrier moving layer has become the mainstream.

By separating the functions in this way, it becomes possible to independently develop materials having the functions of carrier generation and carrier transfer, respectively, and as a result, carriers having various molecular structures can be developed. Many generators and carrier transfer substances have been developed.

Focusing on carrier transfer substances and classifying typical ones among them based on structural characteristics, they are hydrazone type (JP-A-54-59143) and stilbene-styryl type (JP-A-58-198043). , Triarylamine type (Japanese Patent Publication No. 58-32372), phenothiazine type, triazole type, quinoxaline type, oxadiazole type, oxazole type, pyrazoline type, triphenylmethane type, dihydronicotinamide compound, indoline compound, semicarbazone compound, etc. Being developed.

However, despite the fact that many organic compounds have been developed as carrier transfer substances, 1) the compatibility with the binder is low. 2) Crystals are likely to precipitate. 3) A change in sensitivity occurs when it is repeatedly used. 4) Poor chargeability and repeatability. 5) Poor residual potential characteristics. There is no organic compound that satisfies all the problems such as the above, and it is the current situation that one that satisfies the basic properties required for the above-mentioned photoconductor, as well as mechanical strength and durability, has not yet been obtained. Is.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity and high durability. In particular, it is an object of the present invention to provide an electrophotographic photosensitive member which is excellent in stability against temperature and humidity, has high charging characteristics, and maintains high sensitivity characteristics even after repeated use.

[0009]

As a result of repeated studies on photoconductive substances, the inventors of the present invention have high sensitivity and high durability by incorporating a compound having a specific structure into a photosensitive layer. The inventors have found that an electrophotographic photosensitive member can be obtained and completed the present invention.

That is, the electrophotographic photosensitive member of the present invention has the general formula (I)

[Chemical 9] (Here, Ar is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent or a heterocyclic-substituted alkyl group, and n is 2, 3, or 4) is contained in the photosensitive layer formed on the conductive support.

Preferred enamine derivatives represented by the general formula (I) include the general formula (II)

[Chemical 10] (Here, Ar is the same as the above general formula (I)).

Other preferred enamine derivatives represented by the general formula (I) include the general formula (III)

[Chemical 11] (However, R ₁ and R ₂ are the same or different and are a lower alkyl group, an aryl group, an aralkyl group, a heterocyclic group or a heterocyclic alkyl group, or R ₁ and R ₂ are a nitrogen atom together with a nitrogen atom to which they are bonded. May contain a heterocyclic group,
R ₃ , R ₄ , R ₅ and R ₆ are the same or different, and examples thereof include a compound represented by a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower dialkylamine group, and n is 2-4). .

The heterocyclic alkyl group is preferably a thienylmethyl group. R ₁ and R ₂ of the general formula (III)
And the nitrogen-containing heterocyclic group formed by the nitrogen atom bonded to these,

[Chemical 12] It is preferably selected from the group consisting of

Further, R ₁ and R _{2 in} the general formula (III) are
The same or different, a lower alkyl group or an aryl group, or may form a nitrogen-containing heterocyclic group together with the nitrogen atom to which these are bonded, R _{3 of} the general formula (III),
R ₄ , R ₅ and R ₆ are preferably a hydrogen atom or one of them is a lower alkyl group.

It is preferable that the lower alkyl group is a methyl group and the aryl group is a phenyl group.

Another preferred enamine derivative represented by the general formula (I) is the general formula (IV)

[Chemical 13] [In the formula, R ₇ and R ₈ are hydrogen atoms (except when R ₇ and R ₈ are both hydrogen atoms), an aryl group which may have a substituent, and a heterocyclic ring which may have a substituent. A group, an aralkyl group which may have a substituent, a lower alkyl group or a heterocyclic alkyl group, and a is a lower alkyl group, a lower alkoxy group,
It is a halogen atom or a hydrogen atom, m is an integer of 1 to 4 (however, when m is 2 or more, a may be the same or different) n is an integer of 2 to 4. ] The compound shown by these can be mentioned.

The enamine derivative represented by the general formula (IV) is the general formula (V)

Embedded image [In formula, b is a halogen atom, a hydrogen atom, a C1-C5 alkyl group, a C1-C3 alkoxy group, or a C1-C3 dialkylamino group, l is an integer of 1-5. (However, when 1 is 2 or more, b may be the same or different). ] It is preferable that it is a compound shown by these.

Further, the enamine derivative represented by the general formula (IV) has the general formula (VI)

[Chemical 15] [Wherein d is a halogen atom, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 1 to 3 carbon atoms, and r is an integer of 1 to 7] (However, when r is 2 or more, d may be the same or different). ] The compound shown by these may be sufficient.

Further, the enamine derivative represented by the general formula (IV) is a compound represented by the general formula (VII)

Embedded image [In formula, e is a halogen atom, a hydrogen atom, a C1-C5 alkyl group, a C1-C3 alkoxy group, or a C1-C3 dialkylamino group, p is an integer of 1-9. (However, when p is 2 or more, e may be the same or different). ] The compound shown by these may be sufficient.

It is preferable that the photosensitive layer contains a carrier transfer material and a carrier generation material, and the carrier transfer material is an enamine derivative represented by the general formula (I), (III) or (IV).

The photosensitive layer comprises a carrier-generating layer containing a carrier-generating substance and a carrier-moving layer containing a carrier-moving substance, and the carrier-moving substance is represented by the general formula (I), (III) or (IV). It is preferably an enamine derivative.

It is desirable that a surface protective layer is further formed on the photosensitive layer. Further, an intermediate layer made of a polymer material may be formed between the conductive support and the photosensitive layer.

The substituent Ar of the enamine derivative represented by the general formula (I) used in the electrophotographic photoreceptor of the present invention is an aryl group which may have a substituent or a heterocycle which may have a substituent. A group, an aralkyl group which may have a substituent, or a heterocyclic-substituted alkyl group. Specifically, aryl such as phenyl, tolyl, methoxyphenyl, ethoxyphenyl, isopropylphenyl, fluorophenyl, trifluoromethylphenyl, dimethylaminophenyl, naphthyl, methylnaphthyl, biphenyl, methylbiphenyl, methoxybiphenyl, anthryl, tetralinyl and indanyl. Group, pyridyl, pyrimidyl, benzothiofuranyl, fluorenonyl, acridinyl, 2,1,3-benzothiadiazolyl, 2-benzothiadiazolyl, 6-methoxy-2-benzothiadiazolyl, 2-benzoxazolyl , 2-methyl-5-benzoxazolyl, 4-phenyl-2-thiazolyl, 5-ethyl-2-1,3,4
-Thiadiazolyl, a heterocyclic group such as 5-methyl-3-isoxazolyl, an aralkyl group such as benzyl, methoxybenzyl, and methylbenzyl, and a heterocyclic-substituted alkyl group such as thienylmethyl. Substituted aryl groups are effective.

Particularly preferably, phenyl, p-methoxyphenyl, m-methoxyphenyl, p-ethoxyphenyl, m-ethoxyphenyl, p-tolyl, m-tolyl,
m-ethylphenyl, m-isopropylphenyl, 3,
5-xylyl, m-chlorophenyl, 1-naphthyl, m
Examples thereof include an aryl group such as dimethylaminophenyl and a heterocyclic group such as 2-pyridyl, 6-methoxy-2-benzothiazolyl, and 2-methyl-5-benzoxazolyl.

The enamine derivative of the general formula (I) relating to the electrophotographic photoreceptor of the present invention can be synthesized by various methods, but it is usually easily synthesized by the following synthesis process. That is, two equivalents of a primary amine compound represented by the following formula (VIII) and an aldehyde compound represented by the following formula (IX) are heated in an acid catalyst in a solvent such as benzene under an acid catalyst to carry out dehydration condensation. An enamine derivative (I) is obtained.

[Chemical 17]

In the present invention, the above enamine derivative is used as a carrier transfer material for an electrophotographic photoreceptor. Specific examples of the enamine derivative represented by the general formula (I) used in the electrophotographic photoreceptor of the present invention include the exemplified compounds having the substituents shown in Tables 1 to 5 below.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

[Table 5]

[0032]

[Table 6]

[0033]

[Table 7]

[0034]

[Table 8]

[0035]

[Table 9]

[0036]

[Table 10]

[0037]

[Table 11]

[0038]

[Table 12]

[0039]

[Table 13]

[0040]

[Table 14]

[0041]

[Table 15]

Among these exemplified compounds, those having excellent electrophotographic properties, cost and synthetic properties are especially Nos. 1 and 2,
3, 4, 7, 11, 15, 16, 22, 26, 28, 4
2, 56, 57, 58, 59, 63, 67, 78, 8
The compounds are 2, 91, 92, 93, 94, 96 and 97.

Other preferred enamine derivatives represented by the general formula (I) include the general formula (III)

Embedded image (However, R ₁ and R ₂ are the same or different and are a lower alkyl group, an aryl group, an aralkyl group, a heterocyclic group or a heterocyclic alkyl group, or R ₁ and R ₂ are a nitrogen atom together with a nitrogen atom to which they are bonded. R ₃ , which may form a heterocyclic group,
R ₄ , R ₅ and R ₆ are the same or different, and examples thereof include a compound represented by a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower dialkylamine group, and n is 2-4).

This enamine derivative is a compound not described in the literature. The substituents of the enamine derivative represented by the general formula (III) of the present invention will be described. Examples of the lower alkyl group for R ₁ and R ₂ include methyl, ethyl, n-
There are propyl, iso-propyl, n-butyl, sec-butyl, n-pentyl groups and the like. As an aryl group,
For example, phenyl, 1-naphthyl, 9-anthracelyl group and the like can be mentioned. In these aryl groups, at least one hydrogen atom may be substituted with methyl, methoxy, halogen or the like. Examples thereof include p-tolyl, 3,5
-Xylyl, p-methoxyphenyl, p-chlorophenyl, 2-methyl-1-naphthyl group.

The aralkyl group includes, for example, a benzyl group, a phenylethyl group and the like, and those having these substituents include, for example, p-methoxybenzyl and p-.
Methylbenzyl, p-chlorobenzyl group and the like can also be used. Examples of the heterocyclic group include 2-furyl, 3-
Furyl, 2-cenyl, 3-cenyl, 2-pyridyl,
There are 2-benzothiazoyl group, 2-benzoxazolyl group and the like, and those having these substituents can also be used.

Examples of the heterocyclic alkyl group include 2-
There are cenylmethyl, 2-furylmethyl, 3-furylmethyl, 3-cenylmethyl, 2-pyridylmethyl, 2-benzothiazoylmethyl, 2-benzoxazoylmethyl groups, etc., and those having these substituents should also be used. You can Among these, 2-Cenylmethyl,
3-Cenylmethyl group is preferred.

Examples of the nitrogen-containing heterocyclic group formed with the nitrogen atom to which R ₁ and R ₂ are bonded include, for example,

[Chemical 19] Etc.

Of the above substituents, R ₁ and R ₂ are preferably a lower alkyl group or aryl group, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded form a nitrogen-containing heterocyclic group. . The lower alkyl group is particularly preferably a methyl group. The alkyl group is particularly preferably a phenyl group. The nitrogen-containing heterocyclic group is particularly preferably

Embedded image Is preferred.

Further, as those having these substituents,
For example

[Chemical 21] Etc. are also preferable.

R ₃ , R ₄ , R ₅ and R ₆ are the same or different and are preferably a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower dialkylamine group, but a hydrogen atom or an electron-donating substituent Groups are preferred. Examples of the electron-donating substituent include a methyl group, an ethyl group, a propyl group, a methoxy group and a dimethylamino group.

In the present invention, R ₃ , R ₄ , R ₅ and R _{6 are}
Is preferably an enamine derivative in which is a hydrogen atom or one of them is a lower alkyl group. In the present invention, the enamine derivative of the general formula (III) can be synthesized, for example, by the following two methods.

In the first method, as shown in formula (a), first, the 4-nitrobenzaldehyde derivative (X) and the hydrazine derivative (XI) are heated in the presence of a condensation catalyst, for example, in ethanol, A 4-nitrobenzhydrazone derivative (XII) is synthesized.

[Chemical formula 22] Examples of the catalyst include potassium acetate, sodium acetate, acetic acid and the like.

Then, as shown in the formula (b), the 4-nitrobenzhydrazone derivative (XII) is converted into, for example, 1,4
-Reduced with iron powder and acid while heating in a mixed solvent of dioxane / water to give 4-aminobenzhydrazone derivative (XI
II) is synthesized.

[Chemical formula 23] As the above-mentioned acid, for example, acetic acid aqueous solution, hydrochloric acid aqueous solution or the like is used.

Then, as shown in formula (c), the 4-aminobenzhydrazone derivative (XIII) is condensed with the condensed polycyclic hydrocarbon-substituted aldehyde (XIV) in the presence of an acid catalyst while heating, for example, in toluene. Then, the enamine derivative (III) of the target compound is synthesized.

[Chemical formula 24] Examples of the acid catalyst include P-toluenesulfonic acid,
Camphor-sulfonic acid or the like is used.

In the second method, as shown in formula (d), the aniline derivative (XV) and the condensed polycyclic hydrocarbon-substituted aldehyde (XIV) are heated in, for example, toluene in the presence of an acid catalyst. To produce a condensed polycyclic vinylidene-substituted aniline derivative (XVI).

[Chemical 25] Examples of the acid catalyst include P-toluenesulfonic acid,
Camphor-sulfonic acid or the like is used.

Then, as shown in formula (e), the fused polycyclic vinylidene-substituted aniline derivative (XVI) is converted into, for example, N,
Formylation is carried out by treating N-dimethylformamide or N-methyl-N-phenylformamide with phosphorus oxychloride to synthesize a benzaldehyde derivative (XVII).

[Chemical formula 26]

Then, as shown in formula (f), the benzaldehyde derivative (XVII) and the hydrazine derivative (XI) are reacted with a catalyst while heating, for example, in ethanol to give the enamine derivative (III) of the target compound. To synthesize.

[Chemical 27] As the catalyst, for example, acetic acid, potassium acetate or the like is used.

In the present invention, the exemplified compounds shown in Tables 6 to 15 can be synthesized by using the above-mentioned synthesis method and used as a carrier transfer substance for an electrophotographic photoreceptor.

[0059]

[Table 16]

[0060]

[Table 17]

[0061]

[Table 18]

[0062]

[Table 19]

[0063]

[Table 20]

[0064]

[Table 21]

[0065]

[Table 22]

[0066]

[Table 23]

[0067]

[Table 24]

[0068]

[Table 25]

[0069]

[Table 26]

[0070]

[Table 27]

[0071]

[Table 28]

[0072]

[Table 29]

[0073]

[Table 30]

[0074]

[Table 31]

Among the above-exemplified compounds, general formula (III)
One of the substituents R ₁ and R _{2 in} the above is a phenyl group and the other is a methyl group, a phenyl group or a thienylmethyl group

[Chemical 28] The enamine derivative forming the is preferable because it has good electrophotographic properties, low production cost, and easy synthesis.

However, the above-mentioned substituents such as phenyl group, thienylmethyl group,

[Chemical 29] May have a substituent in place of the hydrogen atom.
Examples of this substituent include a methyl group and a methoxy group. In the present invention, the enamine derivative represented by the general formula (III) is used as a carrier transfer substance for an electrophotographic photoreceptor.

Another preferred enamine derivative represented by the general formula (I) is the general formula (IV)

Embedded image [In the formula, R ₇ and R ₈ are hydrogen atoms (except when R ₇ and R ₈ are both hydrogen atoms), an aryl group which may have a substituent, and a heterocyclic ring which may have a substituent. A group, an aralkyl group which may have a substituent, a lower alkyl group or a heterocyclic alkyl group, and a is a lower alkyl group, a lower alkoxy group,
It is a halogen atom or a hydrogen atom, m is an integer of 1 to 4 (however, when m is 2 or more, a may be the same or different) n is an integer of 2 to 4. ] The compound shown by these can be mentioned.

In the definitions of R ₇ and R ₈ in the above general formula (IV), the substituents in the terms "aryl group", "aralkyl group" and "heterocyclic group" include lower alkyl groups such as methyl and ethyl. , Lower alkoxy groups such as methoxy and ethoxy, amino groups such as methylamino, dimethylamino, ethylamino, ethylmethylamino and diethylamino, and halogen atoms such as fluorine atom, chlorine atom and bromine atom. Each of the above groups preferably has one or two of these substituents.

The "aryl group" has 6 to 14 carbon atoms.
And aromatic hydrocarbon residues having, for example, phenyl, naphthyl, anthryl and the like. As the "aralkyl group", a phenyl-C _1-3 alkyl group such as benzyl,
It includes phenethyl and the like. The “heterocyclic group” includes a 6-membered ring having 1 or 2 N atoms and a 5-membered ring having 1 or 2 O, N or S atoms. These heterocyclic groups may be condensed with a benzene ring. Examples thereof include pyridyl, pyrimidinyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl and the like.

Specific examples of the term "aryl group which may have a substituent (s)" in the definition of R ₇ and R ₈ include phenyl and p-
Tolyl, p-ethylphenyl, p-methoxyphenyl,
p-ethoxyphenyl, p-chlorophenyl, p-fluorophenyl, 3,5-xylyl, 3,4-xylyl,
2,5-xylyl, p-dimethylaminophenyl, 1-
Naphthyl, 2-naphthyl, 2-methyl-1-naphthyl,
9-anthryl and the like can be mentioned.

Specific examples of the term "aralkyl group which may have a substituent (s)" in the definition of R ₇ and R ₈ include benzyl, p-
Methylbenzyl, p-methoxybenzyl, p-chlorobenzyl and the like can be mentioned. Specific examples of the term “heterocyclic group optionally having substituent (s)” in the definition of R ₇ and R ₈ include 2-
Benzothiazolyl, 2-benzoxazolyl, 2-pyridyl, 2-thienyl, 3-thienyl, 2-furyl, 3-
Examples include frills.

The term "lower alkyl group" in the definitions of R ₇ and R ₈ is preferably an alkyl group having 1 to 5 carbon atoms,
Specific examples thereof include methyl, ethyl, n-propyl,
Examples thereof include i-propyl, n-butyl, sec-butyl, n-pentyl and the like. Specific examples of the term “heterocyclic alkyl group” in the definitions of R ₇ and R ₈ include 2-thienylmethyl,
2-furylmethyl, 3-furylmethyl, 2-pyridylmethyl, 2-benzothiazoylmethyl, 2-benzoxazoylmethyl and the like can be mentioned.

The term "lower alkyl group" in the definition of a is preferably an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, Examples include sec-butyl and n-pentyl. The term "lower alkoxy group" in the definition of a is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and specific examples thereof include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,
Examples include n-pentoxy and the like.

The enamine derivative of the general formula (IV) of the present invention can be synthesized by various methods. For example, it can be synthesized by the following two methods. That is, the first method is to use a 4-nitrobenzaldehyde derivative having various substituents represented by the following formula (XVIII) and the following formula (XI
The Bittig reagent having various substituents represented by X) is reacted with potassium tert-butoxide in tetrahydrofuran to obtain a styryl derivative represented by the following formula (XX).

[Chemical 31] [In the formula, R ₇ , R ₈ , a and m have the same meaning as defined in formula (IV), and R ₉ is a lower alkyl group or a phenyl group. ]

Next, the styryl derivative (XX) was treated with 1,4-dioxane / hydrochloric acid by using acetic acid, hydrochloric acid or the like as a catalyst.
A reduction reaction with iron in a mixed solvent of water is performed to obtain an aniline derivative represented by the following formula (XXI).

Embedded image [In the formula, m has the same meaning as defined in the general formula (IV). ]

Next, this aniline derivative (XXI) was mixed with an aldehyde compound represented by the following formula (XXII) and toluene,
The enamine derivative represented by the general formula (IV) of the present invention can be obtained by dehydration condensation under an acid catalyst.

[Chemical 33] [In the formula, n has the same meaning as defined in formula (IV). ]

The second method is to prepare an aniline derivative having various substituents represented by the following formula (XXIII) by the following formula (XXI
An enamine derivative represented by the following formula (XXIV) is obtained by dehydration condensation with an aldehyde compound represented by I) in toluene under an acid catalyst.

Embedded image [In the formula, a, m, and n have the same meanings as defined in formula (IV). ]

Then, the enamine derivative represented by the formula (XXIV) is subjected to a formylation reaction with phosphorus oxychloride and N, N-dimethylformamide, N-methyl-N-phenylformamide or the like, and represented by the following formula (XXV). An aldehyde compound is obtained.

Embedded image [In the formula, a, m, and n have the same meanings as defined in formula (IV). ]

Next, the above aldehyde compound (XXV) is reacted with Bittig reagent (XIX) having various substituents and potassium-tert-butoxide in tetrahydrofuran to give an enamine derivative represented by the general formula (IV) of the present invention. Can be obtained.

Embedded image [In the formula, R ₉ has the same meaning as defined above, and R ₇ and R ₈ have the same meaning as defined in formula (IV). ]

In the present invention, for example, the exemplified compounds shown in Tables 16 to 27 below can be synthesized by the above synthesis method and used as a carrier transfer substance for an electrophotographic photoreceptor.

[0091]

[Table 32]

[0092]

[Table 33]

[0093]

[Table 34]

[0094]

[Table 35]

[0095]

[Table 36]

[0096]

[Table 37]

[0097]

[Table 38]

[0098]

[Table 39]

[0099]

[Table 40]

[0100]

[Table 41]

[0101]

[Table 42]

[0102]

[Table 43]

Of the above-mentioned general formula (IV), preferred compounds are those of the formula (V)

Embedded image [In formula, b is a halogen atom, a hydrogen atom, a C1-C5 alkyl group, a C1-C3 alkoxy group, or a C1-C3 dialkylamino group, l is an integer of 1-5. (However, when 1 is 2 or more, b may be the same or different). ] Compound,

Formula (VI)

[Chemical 38] [Wherein d is a halogen atom, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 1 to 3 carbon atoms, and r is an integer of 1 to 7] (However, when r is 2 or more, d may be the same or different). ] Compound

And formula (VII)

[Chemical Formula 39] [In formula, e is a halogen atom, a hydrogen atom, a C1-C5 alkyl group, a C1-C3 alkoxy group, or a C1-C3 dialkylamino group, p is an integer of 1-9. (However, when p is 2 or more, e may be the same or different). ] The compound of these is mentioned.

In the definitions of b, d and e, the term "carbon number 1 to 5"
Specific examples of the “alkyl group of” include methyl, ethyl, n
-Propyl, i-propyl, n-butyl, sec-butyl, n-pentyl and the like. Specific examples of the term "alkoxy group having 1 to 3 carbon atoms" in the definitions of b, d, and e include methoxy, ethoxy, propoxy and the like.

Among these exemplified compounds, those particularly excellent in electrophotographic properties, cost and synthesis are those in which one of R ₇ and R ₈ is a hydrogen atom and the other is phenyl group, p-tolyl group, p -Methoxyphenyl group, p-dimethylaminophenyl group and 1-naphthyl group, or both R ₇ and R ₈ are phenyl groups, and a is a hydrogen atom or an electron-donating substituent, for example, methyl, ethyl, n Alkyl groups such as -propyl, i-propyl, n-butyl, sec-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, i
-Alkoxy groups such as propoxy, n-butoxy, n-pentoxy and the like.

In the present invention, the enamine derivative represented by the general formula (IV) is used as a carrier transfer material for an electrophotographic photoreceptor. The electrophotographic photoreceptor according to the present invention is formed by laminating a photosensitive layer on a conductive support.

The above-mentioned conductive support is for forming a photosensitive layer on the conductive support, applying an electric field to the photosensitive layer, and moving carriers (electrons or holes) generated by light absorption of the photosensitive layer. Therefore, a conductor such as a drum, a plate, or a sheet can be used. As this conductor,
It is possible to use metal, carbon, paper or plastic film that has been subjected to conductive processing. Examples of the metal include copper and aluminum, and examples of the conductive processed paper include, for example, paper in which a carbon material is dispersed, and examples of the conductive processed plastic film, such as aluminum-deposited polyester film and the like. There is.

The above-mentioned photosensitive layer is for forming a latent image (electrostatic latent image) consisting of a two-dimensional distribution of electrostatic charges, and comprises a carrier-generating substance and a carrier-moving substance, and further has a film-forming bond. Agents, spectral sensitizers, electrical property deterioration preventing agents, antioxidants, anti-curl agents, and leveling agents can be contained as appropriate.

The carrier-generating substance is capable of generating a carrier by absorbing light, and for example, a photosensitive pigment or dye can be used. Among these, photosensitive pigments are preferable. Examples of the photosensitive pigment include phthalocyanine-based pigments such as various metal phthalocyanines, metal-free phthalocyanines, and halogenated metal-free phthalocyanines,
There are perylene imide pigments such as perylene imide and perylene anhydride, azo pigments such as bisazo pigments and trisazo pigments, quinacridone pigments and anthraquinone pigments. In particular, a bisazo pigment containing a metal-free phthalocyanine pigment, a titanyl phthalocyanine pigment, phlorenylidene, and a phlorenone ring as a pigment that generates a carrier,
Those using a bisazo pigment or trisazo pigment composed of an aromatic amine can provide an excellent electrophotographic photoreceptor showing high sensitivity.

Examples of the photosensitive dyes include triphenylmethane dyes represented by methyl violet, crystal violet, night blue, Victoria blue and the like, erythrosine, rhodamine B, rhodamine 3R, acridine orange, and flapeosin. Examples include acridine dyes, thiazine dyes represented by methylene blue and methylene green, oxazine dyes represented by capri blue and meldora blue, and other cyanine dyes, styryl dyes, pyrylium salt dyes and thiopyrylium salt dyes. These dyes may be used alone,
The coexistence of the above-mentioned pigments often causes the carrier to be generated with higher efficiency.

The electrophotographic photosensitive member of the present invention exhibits extremely high performance by containing one or more kinds of the compounds represented by the general formula (I) as a carrier transfer substance in the photosensitive layer. In addition, as other carrier transfer substances, β-phenyl- [4- (dibenzylamino)] stilbene, β-phenyl- [4-
(N-Ethyl-phenylamino)] stilbene, 1,1
-Styryl compounds such as bis (4-diethylaminophenyl) -4,4-diphenylbutadiene, 4- (dibenzylamino) benzaldehyde-N, N-diphenylhydrazone, 4- (ethylphenylamino) benzaldehyde-N, N-diphenyl Hydrazone compounds such as hydrazone, 4-di (P-tolylamino) benzaldehyde-N, N-diphenylhydrazone, 3,3-bis [(4'-diethylamino) phenyl] acrolein-N, N-diphenylhydrazone, 4-methoxy- 4 '-(4-methoxystyryl) triphenylamine, 4-methoxy-
A triphenylamine compound such as 4'-styryltriphenylamine may be contained.

The enamine derivative represented by the general formula (I) or the carrier transfer substance in the photoreceptor of the present invention is formed into a film on the conductive support with the aid of a binder resin having a film forming ability. In this case, in order to further increase the sensitivity, it is desirable to add a substance that imparts plasticity to the above-mentioned carrier generating substance and binder resin to form a uniform photoreceptor film. There are various binder resins having film forming ability, depending on the field of application.

That is, in the field of photoconductors for copying machines or printers, polystyrene, polyvinyl acetal, polysulfone, polycarbonate, polyphenylene oxide, polyester, alkyd resin, polyacrylate and the like are preferable. You may use these individually or in mixture of 2 or more types. Among these, resins such as polystyrene, polycarbonate, polyacrylate, and polyphenylene oxide have a volume resistance value of 10 ¹³ Ω or more, and are also excellent in film forming property and potential property.

The amount of these binder resins is 0.1% by weight with respect to the enamine derivative represented by the general formula (I).
It is 2 to 20 times, and preferably 0.5 to 5 times.
If it is less than 0.2 times, the compound is precipitated from the surface of the photoreceptor, and if it exceeds 20 times, the sensitivity is remarkably lowered. An alkaline binder is particularly required for use in the printing plate. The alkaline binder is an acidic group soluble in water or an alcoholic alkaline solvent (including a mixed system), such as an acid anhydride group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group or a sulfonimide group. It is a polymer substance.

These alkaline binders usually have an acid value of 10.
It is preferable to have a high value of 0 or more. These polymer substances having a high acid value, that is, the binder resin, are easily dissolved or easily swelled in an alkaline solvent. Examples of these binder resins include styrene-maleic anhydride copolymers, vinyl acetate-maleic anhydride copolymers, vinyl acetate-crotonic acid copolymers, methacrylic acid-methacrylic acid ester copolymers, phenolic resins, methacrylic acid. Acid-styrene copolymers, styrene-methacrylic acid ester copolymers, methacrylic acid-styrene-methacrylic acid ester copolymers and the like are shown.

In order to further increase the sensitivity, it is preferable to add a substance capable of imparting plasticity to the film forming binder to form a uniform photosensitive film. Examples of the substance capable of imparting plasticity include phthalic acid esters (eg DOP, DBP etc.), phosphoric acid esters (eg TC
P, TOP, etc.), adipic acid ester, nitrile rubber, chlorinated hydrocarbon and the like.

As the above-mentioned spectral sensitizer added to the photosensitive layer, for example, a sensitizing dye is used, and specifically, triphenylmethane represented by methyl violet, crystal violet, night blue, Victoria blue and the like. Dyes, erythrosine, rhodamine B, rhodamine 3
Acridine dye represented by R, acridine orange, flapeosin, etc., thiazine dye represented by methylene blue, methylene green, etc., oxazine dye represented by capri blue, meldra blue, etc., cyanine dye, styryl dye, pyrylium salt dye , Thiopyrylium salt dye, etc.

The above-mentioned electrical property deterioration preventive agent prevents deterioration such as increase in residual potential, decrease in charging potential, decrease in sensitivity, etc., in repeated use of the electrophotographic photoreceptor.
Examples of the substance contained in the photosensitive layer include tribenzylamine, tetrabenzyl-p-xylenediamine, 1-
Chloranthraquinone, benzoquinone, 2,3-dichloronaphthoquinone, naphthoquinone, 4,4'-dinitrobenzophenone, 4,4'-dichlorobenzophenone, 4
-Nitrobenzophenone, 4-nitrobenzalmalondinitrile, α-cyano-β- (p-cyanophenyl) ethyl acrylate, 9-anthracenylmethylmalondinitrile, 1-cyano-1- (p-nitrophenyl ) -2
Examples thereof include electron-withdrawing compounds such as-(p-chlorophenyl) ethylene and 2,7-dinitrofluorenone.

Examples of the above antioxidant include BHT,
BHQ etc. are mentioned. Examples of the leveling agent include silicone oil and the like. The photoreceptor of the present invention is a coating solution prepared by dissolving or dispersing the enamine derivative represented by the general formula (I) in a suitable solvent together with the above-mentioned various additives according to the form of the photoreceptor. A photoconductor is manufactured by coating and drying on the above-mentioned conductive support.

As the coating solvent, benzene, toluene,
Aromatic hydrocarbons such as xylene and monochlorobenzene, and solvents such as dioxane, dimethoxymethyl ether, dimethylformamide, and methylene chloride, alone or 2
A mixed solvent of one or more kinds or a solvent such as alcohols, acetonitrile and methyl ethyl ketone may be further added and used.

In the photoconductor of the present invention, various methods are conceivable for the embodiment using the enamine derivative. For example, a photoconductor in which an enamine derivative is used as a carrier transfer substance, a carrier-generating substance or an electron-withdrawing compound is added, and the product is dissolved or dispersed in a binder resin as a photosensitive layer and coated on a conductive support. You can Further, the photosensitive layer has a laminated structure composed of a carrier generation layer having a high charge generation efficiency and a carrier transfer layer. That is, (sensitization)
On the carrier generating layer mainly composed of dye or pigment, the enamine derivative is dissolved or dispersed in a binder resin by adding an antioxidant compound or an electron-withdrawing compound, if necessary, and laminated as a carrier moving layer. Then, as the photosensitive layer, a photosensitive body obtained by laminating this photosensitive layer on a conductive support can be shown.

Aspects of the electrophotographic photosensitive member of the present invention will be described more specifically schematically with reference to FIGS. FIG.
Is a photosensitive layer 4 on a conductive support 1, a carrier generating layer 5 having a carrier generating substance 2 as a main component dispersed in a binder and a carrier moving substance having a carrier transfer substance 3 as a main component dispersed in a binder. It is a function-separated type photoreceptor comprising a laminate with a layer 6, a carrier transfer layer 6 is formed on the surface of the carrier generation layer 5, and the carrier transfer material 3 is contained in the carrier transfer layer 6.
1 shows a constitution of a photoreceptor using the enamine derivative of the present invention.

FIG. 2 shows a function-separated type photoreceptor having the same carrier generating layer 5 and carrier moving layer 6 as the photoreceptor of FIG. 1, but the charge carrier is opposite to the photoreceptor of FIG. The carrier generating layer 5 is formed on the surface of the moving layer 6, and the constitution of the photoreceptor using the enamine derivative of the present invention as the carrier moving substance 3 in the carrier moving layer 6 is shown.

FIG. 3 shows a photosensitive layer 4'on the conductive support 1.
As carrier generation substance 2 and carrier transfer substance 3
2 shows a constitution of a photoreceptor having a single layer in which is dispersed in a binder. FIG. 4 shows a structure in which a surface protective layer 7 is further provided on the surface of the photoconductor of FIG. 3 and shows the structure of the photoconductor consisting of a single layer.

FIG. 5 shows the structure of a function-separated type photoreceptor in which an intermediate layer 8 is provided between the conductive support 1 and the same photosensitive layer 4 as in FIG. FIG. 6 shows an arrangement in which an intermediate layer 8 is provided between the conductive support 1 and the same photosensitive layer 4'as in FIG. 3, and shows the structure of a single-layer photosensitive body.

A surface protective layer 7 provided on the surface of the photosensitive layer 4.
Is intended to improve durability against mechanical stress and to receive and retain the electric charge of corona discharge in a dark place.It is composed of a chemically stable substance, and the carrier generation layer is exposed to light. It has the ability to transmit light, which transmits light at the time of exposure to reach the carrier generation layer, and it is necessary to neutralize and eliminate the surface charge by receiving the injection of the generated charges. It is required to be as transparent as possible in the wavelength region of maximum absorption.

Materials having such properties include organic insulating film forming materials such as acrylic resins, polyaryls, polycarbonates and urethane resins, and low resistance compounds such as tin oxide and indium oxide to the organic insulating film forming materials. Dispersion, acrylic-modified silicone resin, epoxy-modified silicone resin, alkyd-modified silicone resin, polyester-modified silicone resin, urethane-modified silicone resin and other modified silicone resins, silicone resin as a hard coating agent, to further improve durability For the purpose, a mixed material containing silicon oxide, titanium oxide, indium oxide and zirconium oxide as the main components and a condensate of a silicone resin and a metal alkoxy compound capable of forming a film is suitable.

Further, an organic plasma polymerized film can also be used, and if necessary, oxygen, nitrogen, halogen, and II of the periodic table are used.
It is possible to include I and V group atoms, and it is also possible to form an inorganic material metal, metal oxide, or the like by a method such as vapor deposition or sputtering. The thickness of the surface protective layer is 0.1 μ to 5 μ, preferably 0.5 to 2 μ.
Is.

The intermediate layer 8 provided between the conductive support 1 and the photosensitive layer 4 imparts a protective function and an adhesive function,
The purpose is to improve coatability and to improve charge injection from the substrate to the photosensitive layer.
Casein, polyvinyl butyral, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide are suitable. . The thickness of the intermediate layer is 0.1 to 20 μ.
And preferably 0.5 to 5 μ.

[0132]

EXAMPLES The present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example (Exemplified Compound No. 1) P-methoxyaniline and 2 equivalents of 1-formyl-1,
2,3,4-Tetrahydronaphthalene is heated in benzene using p-toluenesulfonic acid as a catalyst for dehydration condensation and recrystallized with ethanol / ethyl acetate to give a melting point of 1
A compound having a temperature of 64.0 to 166.0 ° C was obtained. The obtained compound was confirmed to be Exemplified Compound No. 1 by ¹³ C-NMR spectrum.

[0134] Figure 7 is normal ¹³ C-NMR spectrum, Figure 8 is a ¹³ C-NMR spectrum by DEPT-135. The two spectra shown in FIG. 7 and FIG. 8 show 5 peaks that characterize Exemplified Compound No. 1.
At 5.61 ppm, a methoxy group, 23.03, 27.15,
Three methylene groups are observed at 30.31 ppm each.

Example 1 An aluminum vapor-deposited polyester film (film thickness 80 μ) was used as a support, and the following structural formula

[Chemical 40] The bisazo pigment represented by is added to a 1% tetrahydrofuran (THF) solution in which a phenoxy resin (manufactured by Union Carbide Co .; "PKHH") is dissolved in the same amount as the resin by weight, and then in a paint conditioner (manufactured by Red Devil). The glass beads having a diameter of 1.5 mm were dispersed together for about 2 hours, applied by the doctor blade method, and dried. The film thickness after drying was 0.2μ.

On this pigment layer (charge carrier generating layer), 1 g of Exemplified Compound No. 1 of the present invention and 1.2 g of polyarylate [manufactured by Unitika Ltd .; "U-100"] were dissolved in methylene chloride. A 15% solution was applied with a squeegee doctor to prepare a resin-enamine derivative solid solution phase (charge carrier transfer layer) having a dry film thickness of 25 μm, and a laminated electrophotographic photoreceptor was obtained.

The electrophotographic characteristics of this laminated type electrophotographic photosensitive member were evaluated by an electrostatic recording paper test apparatus (Kawaguchi Denki; SP-428). Measurement conditions were applied voltage: -6 kV, static: No. 3, white light irradiation (irradiation light: 5 lu
x) exposure amount E ₁₀₀ (lux seconds) required to attenuate from −700 V to −100 V and initial potential V
₀ (-volt) was measured and the value is shown in Table 25. Further, using the same device, charge-discharge (charge removal light: white light 40
The initial potential V ₀ (−−V) and E after the same operation was performed 10,000 times with 1 cycle of irradiating with looks for 1 second)
₁₀₀ (lux · sec) was measured, and changes in V ₀ and E ₁₀₀ (sensitivity repeating characteristics) were examined. The results are shown in Table 28.

Synthesis Example 2 (Exemplified Compound No. 3) p-Methylaniline and 2 equivalents of 1-formyl-1,2,
3,4-Tetrahydronaphthalene is heated in benzene with p-toluenesulfonic acid as a catalyst for dehydration condensation and recrystallized from ethanol / ethyl acetate to give a melting point of 125.
A compound at ˜126 ° C. was obtained. The obtained compound is ¹³ C-N
It was confirmed from the MR spectrum that it was Exemplified Compound No. 3.

FIG. 9 shows a typical ¹³ C-NMR spectrum,
FIG. 10 is a ¹³ C-NMR spectrum by DEPT-135. In the two spectra shown in FIGS. 9 and 10, as a peak characterizing Exemplified Compound No. 3, a methyl group at 20.55 ppm, 23.00, 27.
Three methylene groups are respectively observed at 18,30.31 ppm.

Synthesis Example 3 (Exemplified Compound No. 16) p-ethoxyaniline and 2 equivalents of 1-formyl-1,
2,3,4-Tetrahydronaphthalene was heated in benzene using p-toluenesulfonic acid as a catalyst, dehydrated and condensed, and recrystallized from ethanol / ethyl acetate to obtain a compound having a melting point of 172 to 173 ° C. The compound obtained is ¹³
It was confirmed by C-NMR spectrum that the compound was Exemplified Compound No. 16.

FIG. 11 shows the normal¹³C-NMR spectrum
Fig. 12 is according to DEPT-135 ¹³C-NMR spectrum
It's Koutor. 2 shown in FIGS. 11 and 12
Characterize Exemplified Compound No. 16 in one spectrum
As peak, methyl of ethoxy group at 14.91ppm
Group, 63.84 ppm of ethoxy methylene group, 23.
03, 27.15 and 30.34 ppm each contain 3 samples
Tylene groups are observed.

Synthesis Example 4 (Exemplified Compound No. 26) 3,4- (methylenedioxy) aniline and 2 equivalents of 1-
Formyl-1,2,3,4-tetrahydronaphthalene was heated in benzene using p-toluenesulfonic acid as a catalyst for dehydration condensation and recrystallized from ethanol / ethyl acetate to obtain a compound having a melting point of 155 to 156 ° C. The obtained compound was identified as No. 1 by the ¹³ C-NMR spectrum.
It was confirmed to be 26.

[0143] Figure 13 is a normal ¹³ C-NMR spectrum, and FIG. 14 is a ¹³ C-NMR spectrum by DEPT-135. 2 shown in FIGS. 13 and 14
The two spectra show that the peak characterizing Exemplified Compound No. 26 is a dioxymethylene group at 101.11 ppm, 2
Three methylene groups are observed at 3.03, 27.15, and 30.31 ppm, respectively.

Examples 2 to 7 The exemplified compounds are No. 3, No. 16, No. 26, No. 28 and No.
The same procedure as in Example 1 was carried out except that the number was changed to 58 or No. 86. The results are shown in Table 28.

[0145]

[Table 44]

From Table 28, it was found that the enamine derivative of the present invention had good sensitivity repeating characteristics.

Example 8 0.4 g of x-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc .: "Fast Gemble-8120") on a polyester film vapor-deposited on aluminum was used as a vinyl chloride / vinyl acetate copolymer resin. [Sekisui Chemical Co., Ltd .: "S-Rex M"] 0.3 g was added to 30 ml of an ethyl acetate solution, dispersed in a paint conditioner for about 20 minutes, applied by the doctor blade method, and dried. The carrier generation layer was formed to have a film thickness of 0.4 μm.

Exemplified Compounds on this Charge Carrier Generation Layer
A polyarylate layer containing 50% by weight of the No. 4 enamine derivative was laminated to prepare a photoreceptor having a two-layer structure. Energy (E ₅₀ ) and initial potential (-V ₀ ) required to reduce the potential to half using the 780 nm spectral light of the present photoreceptor
Was obtained, V ₀ = 880 (volt), E ₅₀ = 2.
The photosensitive member had a very high sensitivity of 9 (ergs / cm ² ), and was highly charged.

A laser printer (WD-580P) manufactured by Sharp Corporation was remodeled, the photosensitive member was attached to the drum portion, and continuous blank copy (Non Copy Aging) was performed 10,000 times. The degree of decrease was investigated. As a result, V _o = 870 (volt) and E ₅₀ = 2.9 (erg / cm ² ), which showed almost no change in the values compared with the first time.

Examples 9 to 12 Anodized aluminum substrate surface (alumite layer: 7)
μ) on the support, the above exemplified compounds No. 11 and No. 4
6, 1 g of No. 91 or No. 93, 1.1 g of polyarylate represented by the following structural formula and N, N-3,5-xylyl-3,4-xylyl-3,4,9,10-perylenetetra A solution obtained by dissolving 0.15 g of carboxylimide and 0.05 g of an ultraviolet absorber in methylene chloride (the imide compound was partially dispersed) was applied with an applicator to obtain a single-layer photoconductor having a dry film thickness of 20 μm.

Embedded image

Thus, the electrophotographic characteristics of the photoconductor were measured by the electrostatic recording paper test apparatus. The measurement conditions were as follows: applied voltage: +5.5 kV, static: No.3. The exposure amount E ₁₀₀ (lux · sec) required to reduce from +700 V to +100 V by white light irradiation was measured, and the value is shown in Table 29. Further, the blank copy test was performed 10,000 times, and the degree of decrease in sensitivity (E ₁₀₀ ) is also shown in Table 29.

[0152]

[Table 45]

It was found that the photoconductor using the enamine derivative of the present invention is a photoconductor having excellent sensitivity and repetitive characteristics even in positive charging.

Examples 13 to 17 Exemplified compounds of the present invention No. 1, No. 3, No. 28, No. 58,
No. 86 was used to prepare a laminated electrophotographic photosensitive member under the same conditions as those prepared in Examples 1, 2, 5, 6, and 7, and the temperature was measured by an electrostatic recording paper tester (Kawaguchi Electric SP-428). 35
The electrophotographic characteristics were evaluated under the environment of ° C and humidity of 85%.

The measurement conditions were applied voltage: -6 kV, static: No. 3, and the initial potential V _o (-volt) was measured, and the values are shown in Table 30. Furthermore, it is used in the same device, and electrification-static elimination (charge elimination light, irradiation with white light at 40 lux for 1 second)
The initial potential V _o (−volt) after performing the same operation 10,000 times with 1 cycle as the cycle, and the change of V _o was investigated.
The results are shown in Table 30.

[0156]

[Table 46]

From Table 30, it was found that the enamine derivative of the present invention has excellent stability against temperature and humidity.

Synthesis Example (Exemplified Compound No. 130) By heating p-nitrobenzaldehyde and N, N-diphenylhydrazine hydrochloride in ethanol using a potassium acetate catalyst, p-nitrobenzaldehyde-
Obtain N, N-diphenylhydrazone. Then, this compound was subjected to reduction reaction with iron powder in a 1,4-dioxane / water mixed catalyst to obtain p-aminobenzaldehyde-N, N.
-Obtain diphenylhydrazone. Then, this compound is dehydrated and condensed with 2 equivalents of 1-formyl-1,2,3,4-tetrahydronaphthalene in toluene to obtain Exemplified Compound No. 130 (melting point: 154 to 156 ° C) (note that recrystallization is ethanol. / Ethyl acetate).

The obtained compound was identified as Exemplified Compound No. 130 by measuring ¹³ C-NMR spectrum. Figure 15 is a normal ¹³ C-NMR spectrum, Figure 16 is due to DEPT-135 ¹³ C-NMR
It is a spectrum. From these two spectra, 22.9 was obtained as a signal characterizing Exemplified Compound No. 130.
Three methylene groups are observed at 7, 27.21 and 30.29 ppm, respectively.

Example 18 An aluminum vapor-deposited polyester film (thickness 80 μm) was used as a conductive support, on which the following structural formula was applied.

Embedded image The bisazo pigment represented by is added to a 1% THF solution of a phenoxy resin (manufactured by Union Carbide; PKHH) in the same amount as the resin by weight, and then glass beads having a diameter of 1.5 mm in a paint conditioner (manufactured by Red Devil). At the same time, dispersion was carried out for about 2 hours, and the solution was applied by the doctor blade method and dried to form a pigment layer (carrier generation layer).
The film thickness after drying was 0.2μ.

On this pigment layer (carrier generation layer),
A 15% solution prepared by dissolving 1 g of Exemplified Compound No. 130 and 1.2 g of a polyarylate resin (U-100, manufactured by Unitika Ltd.) in methylene chloride was applied using a squeegee doctor to give an enamine derivative solid having a dry film thickness of 25 μm. A liquid phase (carrier moving layer) was created. The electrophotographic characteristics of the thus-prepared laminated electrophotographic photosensitive member were measured by an electrostatic recording paper tester (Kawaguchi Electric Co., Ltd .; SP-428).

The measurement conditions were applied voltage: -6 kV, static: No. 3, exposure amount E ₁₀₀ (lux seconds) required to attenuate from -700 V to -100 V by white light irradiation (irradiation light: 51 ux), and The initial potential V _o (−volt) was measured, and the value is shown in Table 31. Furthermore, using the same device, electrification-elimination (elimination light: white light 40 lux 1
(Second irradiation) as one cycle and after performing the same operation 10,000 times, the initial potential V _o (-volt) and E ₁₀₀ (lux.
Second) was measured and changes in V _o and E ₁₀₀ were examined. The results are shown in Table 31.

Examples 19 to 22 Instead of using Exemplified Compound No. 130 as the hydrazone derivative in Example 18, No. 111 (Example 19),
No. 195 (Example 20), No. 200 (Example 21) or No. 147 (Example 22) is used, and the others are Example 1
Each electrophotographic photosensitive member was prepared in the same manner as in 8, and the characteristics were measured. The measurement results are shown in Table 31.

[0164]

[Table 47]

From Table 31, it was found that any of these enamine derivatives can produce an electrophotographic photosensitive member having good sensitivity repeating characteristics.

Example 23 On a polyester film vapor-deposited on aluminum, x-type metal-free phthalocyanine (manufactured by Dainippon Ink & Co .; Fast Gemble-
8120) 0.4 g of vinyl chloride / vinyl acetate copolymer resin (Sekisui Chemical Co., Ltd .; S-Rex M) was added to 30 ml of an ethyl acetate solution containing 0.3 g, and the mixture was dispersed in a paint conditioner for about 20 minutes, and then a doctor. A carrier generation layer was formed by coating by the blade method so that the film thickness after drying was 0.4 μm.

Exemplified Compound N is formed on the carrier generation layer.
A polyarylate layer (carrier transfer layer) containing 50% by weight of the enamine derivative of o.127 was laminated to prepare a photoreceptor having a two-layer structure. The energy (E ₅₀ ) required to reduce the potential to half and the initial potential (−V _o ) were determined using the light of 780 nm of the photoconductor, and V _o = 880 (volt), E ₅₀ = 2.1 ( It was a photoreceptor with a very high sensitivity of erg / cm ² ) and a high charging property. In addition, we remodeled Sharp Laser Printer (WD-580P),
Attach this photoconductor to the drum part, and perform continuous blank copy (Non Co
py Aging) was performed 10,000 times, and the degree of initial potential drop and sensitivity drop was examined. The results show that V _o = 875 (volt) and E ₅₀ = 2.1 (erg / cm ² ), almost no change in values was observed compared to the first time, and that the repeatability was good.

Example 24 The surface of an aluminum substrate was anodized (alumite layer: 7).
1) of the enamine derivative No. 117, a polyarylate resin of the following structural formula 1.
1 g and 0.15 g of N, N-3.5-xylyl-3,4-xylyl-3,4,9,10-perylenetetracarboxylic imide and 0.05 g of UV absorber were dissolved in methylene chloride (the imide compound was The solution (partially dispersed state) was applied with an applicator to obtain a single-layer electrophotographic photosensitive member having a dry film thickness of 20 μm.

[Chemical 43]

In this way, the electrophotographic characteristics of the photoconductor were measured by the electrostatic recording paper test apparatus. Measurement conditions are applied voltage:
+5.5 kV, static: No. 3 was used. The exposure amount E ₁₀₀ (lux seconds) required to reduce from +700 V to +100 V by white light irradiation was measured, and the value is shown in Table 32. Further, the blank copy test was performed 10,000 times, and the degree of reduction in sensitivity (E ₁₀₀ ) is also shown in Table 32.

Examples 25 to 29 Compounds exemplified as enamine derivatives in Example 24
Instead of using No. 117, No. 140 (Example 25), N
o.177 (Example 26) and No. 187 (Example 27)
And the other conditions were obtained in the same manner as in Example 24, and the characteristics were measured. The measurement results are shown in Table 32.

[0171]

[Table 48]

It has been found that any electrophotographic photosensitive member using the above enamine derivative has excellent sensitivity in positive charging and has good repeating characteristics.

Examples 28 to 32 Exemplified compounds of the present invention No. 130, No. 111, No. 19
5, No. 200, No. 147, a laminated electrophotographic photosensitive member was prepared under the same conditions as those prepared in Examples 18 to 22, and an electrostatic recording paper test apparatus (Kawaguchi Denki SP-428) was used. The electrophotographic characteristics were evaluated in an environment of a temperature of 35 ° C. and a humidity of 85%. The measurement conditions were an applied voltage of −6 kV and static No. 3, and the initial potential V _o (−volt) was measured, and the values are shown in Table 33. Further, by using the same apparatus, the initial potential V _o after carrying out the same operation 10,000 times with charge-elimination (charge elimination light; irradiation with white light at 40 lux for 1 second) as one cycle
(- V) were measured and examined the change of V _o.

[0174]

[Table 49]

From Table 33, it was found that the enamine derivative of the present invention was excellent in stability against temperature and humidity.

Synthesis Example (Exemplified Compound No. 261) P- (dimethylamino) benzaldehyde was added to potassium-
In the presence of t-butoxide in tetrahydrofuran, p-
React with diethyl nitrobenzylphosphonate, 4-
(Dimethylamino) -4'-nitrostilbene was obtained.
Then, this compound was subjected to a reduction reaction with a hydrochloric acid catalyst and iron powder in a mixed solvent of 1,4-dioxane / water to obtain 4- (dimethylamino) -4'-aminostilbene. This compound was then added to 1-formyl-1,2,3,3 in toluene.
Exemplified Compound No. 261 (melting point 201-203 was obtained by dehydration condensation with 2 equivalents of 4-tetrahydronaphthalene.
° C).

The obtained compound was identified as Exemplified Compound No. 261 by measuring ¹³ C-NMR spectrum. That is, FIG. 17 shows a usual ¹³ C-NMR spectrum, and FIG. 18 shows ¹³ C according to DEPT-135.
-NMR spectrum. As signals characterizing Exemplified Compound No. 261 from the two spectra in FIGS. 17 and 18, 23.00, 27.21, 30.28 ppm
3 methylene groups, and carbon belonging to the N-methyl group was observed at 40.48 ppm.

Examples 33 to 37 A polyester film (thickness 80 μm) vapor-deposited on aluminum was used as a support, and the following structural formula

[Chemical 44] The bisazo pigment represented by the formula (1) was added to a 1% THF solution containing a phenoxy resin (manufactured by Union Carbide; PKHH) in the same amount by weight, and then added in a paint conditioner (manufactured by Red Devil) with a diameter of 1.5 mm. The glass beads were dispersed together for about 2 hours, applied by the doctor blade method, and dried. The film thickness after drying is 0.2μ
Met.

On the pigment layer (carrier generation layer), the exemplified compounds No. 226, No. 234, No. 261, N of the present invention were formed.
A 15% solution of 1.2 g of polyarylate resin (Unitika U-100; 1.2 g) of each of o.280 and No.297 in methylene chloride was applied with a squeegee doctor to obtain a resin having a dry film thickness of 25 μm. An enamine derivative solid solution phase (carrier transfer layer) was prepared. The electrophotographic characteristics of the thus-prepared laminated electrophotographic photosensitive member were measured by an electrostatic recording paper tester (Kawaguchi Electric Co., Ltd .; SP-428). Measurement conditions are as follows: Applied voltage: -6kV, Static: N
It is o.3 and is -7 by white light irradiation (irradiation light: 5lux).
Exposure amount E required to attenuate from 00V to -100V
₁₀₀ (lux · sec) and an initial potential V _o (- V) were measured. The values in Table 34.

Further, using the same apparatus, the initial potential V _o ( _-volt ) after carrying out the same operation 10,000 times with charge-discharge (charge removal light: irradiation with white light at 40 lux for 1 second) as one cycle ) And the exposure dose E ₁₀₀ (lux · sec) were measured, and V _o
And changes in E ₁₀₀ were investigated.

[0181]

[Table 50]

From Table 34, it was found that the enamine derivative of the present invention had good sensitivity and repeatability.

Example 38 An x-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals; Fast Gemble-
8120) 0.4 g was added to 30 ml of an ethyl acetate solution in which 0.3 g of vinyl chloride: vinyl acetate copolymer resin (Sekisui Chemical Co., Ltd .; S-Rex M) was dissolved, and the mixture was dispersed in a paint conditioner for about 20 minutes, It was applied by the doctor blade method, and a carrier generation layer was formed so that the film thickness after drying was 0.4 μm.

Exemplified compound N is formed on the carrier generation layer.
A polyarylate layer containing 50% by weight of the enamine derivative of o.258 was laminated to prepare a photoreceptor having a two-layer structure. The energy (E ₅₀ ) required to halve the potential of the photoconductor and the initial potential V were obtained by using the light of 780 nm spectrum.
_{When o} (-volt) was determined, it was a photoreceptor having a very high sensitivity of V _o = 870 (volt) and E ₅₀ = 2.0 (erg / cm ² ), and was highly charged. In addition, we modified Sharp's laser printer (WD-580P), stuck this photoconductor to the drum section, and performed continuous blank copy (Non Copy).
Aging) was performed 10,000 times, and then the degree of initial potential drop and sensitivity drop was examined. As a result, V _o = 865 (volt) and E ₅₀ = 2.0 (erg / cm ² ), which showed almost no change in the values compared with the first time.

Examples 39 to 42 The surface of an aluminum substrate was anodized (alumite layer: 7).
μ) on the supported substrate, the exemplary compound of the present invention No. 225, N
No. 260, No. 262, No. 294, 1 g each, polyarylate resin 1.1 g and N, N- represented by the structural formula below.
3.5-xylyl-3,4-xylyl-3,4,9,1
A solution of 0.15 g of 0-perylene tetracarboxylic imide and 0.05 g of an ultraviolet absorber dissolved in methylene chloride (the imide compound is partially dispersed) was applied with an applicator to obtain a single-layer photoconductor having a dry film thickness of 20 μm. .

Embedded image

In this way, the electrophotographic characteristics of the photoconductor were measured by the electrostatic recording paper test apparatus. The measurement conditions were as follows: applied voltage: +5.5 kV, static: No.3. The exposure dose E ₁₀₀ (lux · sec) required to reduce from +700 V to +100 V by white light irradiation was measured, and the value is shown in Table 35. Further, the blank copy test was performed 10,000 times, and the degree of reduction in sensitivity (E ₁₀₀ ) is also shown in Table 35.

[0187]

[Table 51]

It was found that the photoconductor using the enamine derivative of the present invention is a photoconductor having excellent sensitivity and repetitive characteristics even in positive charging.

Examples 43 to 47 Exemplified Compounds of the Invention No. 226, No. 234, No. 26
1, No. 280, No. 297, and a laminated electrophotographic photosensitive member was prepared under the same conditions as those prepared in Examples 33 to 37.
Using an electrostatic recording paper test device (SP-428 manufactured by Kawaguchi Denki Co., Ltd.), electrophotographic characteristics were evaluated under the environment of a temperature of 35 ° C. and a humidity of 85%. The measurement conditions were an applied voltage of -6 kV and static No. 3. The initial potential V _o (−volt) was measured and the value is shown in Table 36. Further, using the same device, electrification-elimination (elimination light: irradiation with white light at 40 lux for 1 second)
The after the 10,000 same operation as one cycle, the initial potential V _o - examine changes in (volts) measured V _o Table 36
It was shown to.

[0190]

[Table 52]

From Table 36, it was found that the enamine derivative of the present invention was excellent in stability against temperature and humidity.

[0192]

The electrophotographic photoreceptor having a photoreceptor containing the enamine derivative of the present invention as a carrier transfer substance has high sensitivity and high durability. Compared to the conventional inorganic type, it is non-toxic, has no problems with resources, has good transparency, is lightweight, is easy to form a film, and has both positive and negative charging properties. In addition to having the advantage of an organic photoconductor that it is easy to use, it has excellent characteristics such as excellent stability against temperature and humidity, high charging characteristics, and almost no deterioration in photosensitivity even after repeated use. .

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing a laminated electrophotographic photosensitive member in which a photosensitive layer includes a carrier generating layer and a carrier moving layer.

FIG. 2 is a cross-sectional view schematically showing a layer structure opposite to that of the laminated electrophotographic photoreceptor of FIG.

FIG. 3 is a cross-sectional view schematically showing an electrophotographic photosensitive member having a single photosensitive layer.

4 is a cross-sectional view schematically showing an electrophotographic photosensitive member in which a surface protective layer is provided on the photosensitive layer of FIG.

5 is a cross-sectional view schematically showing an electrophotographic photosensitive member in which an intermediate layer is interposed between the photosensitive layer of FIG. 1 and a conductive support.

FIG. 6 is a cross-sectional view schematically showing an electrophotographic photosensitive member in which an intermediate layer is interposed between the photosensitive layer of FIG. 3 and a conductive support.

FIG. 7: Conventional ¹³ C-NM of Exemplified Compound No. 1 of the present invention
It is an R spectrum.

FIG. 8: DEPT-135 of Exemplified Compound No. 1 of the present invention
^{13 is a 13} C-NMR spectrum according to.

FIG. 9: Conventional ¹³ C-NM of Exemplified Compound No. 3 of the present invention
It is an R spectrum.

FIG. 10: DEPT-13 of Exemplified Compound No. 3 of the present invention
^{13 is a 13} C-NMR spectrum according to Example 5.

FIG. 11 shows the usual ¹³ C- of the exemplified compound No. 16 of the present invention.
It is an NMR spectrum.

FIG. 12: DEPT-1 of Exemplified Compound No. 16 of the Present Invention
^{13 is a 13} C-NMR spectrum according to No. 35.

FIG. 13 shows conventional ¹³ C- of exemplary compound No. 26 of the present invention.
It is an NMR spectrum.

FIG. 14: DEPT-1 of Exemplified Compound No. 26 of the Present Invention
^{13 is a 13} C-NMR spectrum of 35.

FIG. 15: Typical ¹³ C of Exemplified Compound No. 130 of the present invention
-NMR spectrum.

FIG. 16: DEPT- of Exemplified Compound No. 130 of the Present Invention
^{13 is a 13} C-NMR spectrum by 135.

FIG. 17: Conventional ¹³ C of exemplary compound No. 261 of the present invention
-NMR spectrum.

FIG. 18: DEPT- of Exemplified Compound No. 261 of the Present Invention
^{13 is a 13} C-NMR spectrum by 135.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Carrier generating substance 3 Carrier moving substance 4 Photosensitive layer 4'Photosensitive layer 5 Carrier generating layer 6 Carrier moving layer 7 Surface protective layer 8 Intermediate layer

Claims (20)

[Claims] 1. In a photosensitive layer formed on a conductive support, a compound represented by the general formula (I): (Here, Ar is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent or a heterocyclic-substituted alkyl group, and n is 2, 3 or 4) is contained in the electrophotographic photosensitive member. 2. The enamine derivative represented by the general formula (I) is represented by the general formula (II): (Here, Ar is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent or a heterocyclic-substituted alkyl group). The electrophotographic photosensitive member according to claim 1, wherein 3. The enamine derivative represented by the general formula (I) is represented by the general formula (III): (However, R ₁ and R ₂ are the same or different and are a lower alkyl group, an aryl group, an aralkyl group, a heterocyclic group or a heterocyclic alkyl group, or R ₁ and R ₂ are a nitrogen atom together with a nitrogen atom to which they are bonded. May contain a heterocyclic group,
R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each is represented by a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower dialkylamine group, and n is 2-4).
The electrophotographic photosensitive member described. 4. The electrophotographic photosensitive member according to claim 3, wherein the heterocyclic alkyl group is a thienylmethyl group. 5. The nitrogen-containing heterocyclic group formed by R ₁ and R ₂ of the general formula (III) and a nitrogen atom bonded to them is represented by: The electrophotographic photosensitive member according to claim 3, which is selected from the group consisting of: 6. R ₁ and R _{2 in} the general formula (III) are the same or different and each is a lower alkyl group or an aryl group, and R ₃ , R ₄ and R _{5 in the} general formula (III). The electrophotographic photosensitive member according to claim 3, wherein R ₆ and R ₆ are hydrogen atoms or one of them is a lower alkyl group. 7. R ₁ and R ₂ of the general formula (III) together with the nitrogen atom to which they are bonded form a nitrogen-containing heterocyclic group, and R ₃ , R ₄ of the general formula (III), The electrophotographic photosensitive member according to claim 3, wherein R ₅ and R ₆ are hydrogen atoms or one of them is a lower alkyl group. 8. The lower alkyl group is a methyl group,
The electrophotographic photosensitive member according to claim 3, wherein the aryl group is a phenyl group. 9. The enamine derivative represented by the general formula (I) has the general formula (IV): [In the formula, R ₇ and R ₈ are hydrogen atoms (except when R ₇ and R ₈ are both hydrogen atoms), an aryl group which may have a substituent, and a heterocyclic ring which may have a substituent. A group, an aralkyl group which may have a substituent, a lower alkyl group or a heterocyclic alkyl group, and a is a lower alkyl group, a lower alkoxy group,
It is a halogen atom or a hydrogen atom, m is an integer of 1 to 4 (however, when m is 2 or more, a may be the same or different) n is an integer of 2 to 4. ] The electrophotographic photoreceptor according to claim 1, represented by 10. The enamine derivative represented by the general formula (IV) has the general formula (V): [In formula, b is a halogen atom, a hydrogen atom, a C1-C5 alkyl group, a C1-C3 alkoxy group, or a C1-C3 dialkylamino group, l is an integer of 1-5. (However, when 1 is 2 or more, b may be the same or different). ] The electrophotographic photoconductor of Claim 9 shown by these. 11. The enamine derivative represented by the general formula (IV) has the general formula (VI): [Wherein d is a halogen atom, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 1 to 3 carbon atoms, and r is an integer of 1 to 7] (However, when r is 2 or more, d may be the same or different). ] The electrophotographic photoconductor of Claim 9 shown by these. 12. The enamine derivative represented by the general formula (IV) is represented by the general formula (VII): [In formula, e is a halogen atom, a hydrogen atom, a C1-C5 alkyl group, a C1-C3 alkoxy group, or a C1-C3 dialkylamino group, p is an integer of 1-9. (However, when p is 2 or more, e may be the same or different). ] The electrophotographic photoconductor of Claim 9 shown by these. 13. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer contains a carrier transfer substance and a carrier generation substance, and the carrier transfer substance is an enamine derivative represented by the general formula (I). 14. The electrophotographic photosensitive member according to claim 3, wherein the photosensitive layer contains a carrier transfer material and a carrier generation material, and the carrier transfer material is an enamine derivative represented by the general formula (III). 15. The electrophotographic photosensitive member according to claim 9, wherein the photosensitive layer contains a carrier transfer material and a carrier generation material, and the carrier transfer material is an enamine derivative represented by the general formula (IV). 16. The photosensitive layer comprises a carrier generating layer containing a carrier generating substance and a carrier transferring layer containing a carrier transferring substance, and the carrier transferring substance is an enamine derivative of the general formula (I). 1. The electrophotographic photosensitive member according to 1. 17. The photosensitive layer comprises a carrier generation layer containing a carrier generation substance and a carrier transfer layer containing a carrier transfer substance, and the carrier transfer substance is an enamine derivative of the general formula (III). 3. The electrophotographic photosensitive member according to item 3. 18. The photosensitive layer comprises a carrier generation layer containing a carrier generation substance and a carrier transfer layer containing a carrier transfer substance, and the carrier transfer substance is an enamine derivative represented by the general formula (IV). 9. The electrophotographic photosensitive member according to item 9. 19. The electrophotographic photosensitive member according to claim 1, wherein a surface protective layer is further formed on the photosensitive layer. 20. The electrophotographic photosensitive member according to claim 1, wherein an intermediate layer made of a polymer substance is formed between the conductive support and the photosensitive layer.