JP3433582B2 - Electrophotographic photoreceptor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor for electrophotography. More specifically, it relates to a very sensitive and high-performance electrophotographic photoreceptor having a photosensitive layer containing an organic photoconductive substance.

[0002]

2. Description of the Related Art Conventionally, inorganic photoconductive substances such as selenium, cadmium sulfide and zinc oxide have been widely used in the photosensitive layer of electrophotographic photoreceptors. However, selenium and cadmium sulfide need to be recovered as poisons, selenium has poor heat resistance because it is crystallized by heat, cadmium sulfide and zinc oxide have poor moisture resistance, and zinc oxide has no printing durability. However, the efforts for developing a new photoconductor have been continued. Recently, studies have been conducted on the use of organic photoconductive materials in the photosensitive layer of electrophotographic photoconductors, and some of them have been put to practical use. Organic photoconductive materials are lighter than inorganic ones, are easier to form films, are easier to manufacture photoconductors, and depending on the type, materials that can produce transparent photoconductors are pollution-free It has advantages such as

Recently, a so-called function-separated type photoconductor, in which separate functions of charge carrier generation and transfer are shared by different compounds, has become the mainstream of development because it is effective for high sensitivity. The organic photoconductor is also put into practical use. As the charge carrier transport medium, there are a case where a high molecular weight photoconductive compound such as polyvinylcarbazole is used and a case where a low molecular weight photoconductive compound is dispersed and dissolved in a binder polymer.

[0004]

In particular, organic low-molecular-weight photoconductive compounds can easily select mechanical properties as a binder because they have excellent film-forming properties, flexibility and adhesive properties. (See Japanese Patent Application Laid-Open No. 60-196767, Japanese Patent Application Laid-Open No. 60-218652, Japanese Patent Application Laid-Open No. 60-2331).
56, JP-A-63-48552, JP-A-1
-267552, Japanese Patent Publication No. 3-39306,
JP-A-3-113459 and JP-A-3-12335.
No. 8, JP-A-3-149560, JP-A-6-
273950, etc.). However, it has been difficult to find a compound suitable for producing a highly sensitive photoreceptor.

Further, in the continuous demand for high sensitivity,
In terms of electrical characteristics, there are various problems such as insufficient residual potential, poor photoresponsiveness, deterioration of chargeability after repeated use, and accumulation of residual potential. There has been reported a technique (Japanese Patent Application Laid-Open No. 61-134767) that uses a combination of hydrazone compounds to prevent the residual potential from increasing without significantly impairing other properties of the photoreceptor. However, the balance of the characteristics is not always sufficient, and there has been a demand for a technique for improving the characteristics of the photoreceptor as a whole in a well-balanced manner.

Further, a semiconductor laser has been positively applied in the printer field as a light source. In this case, the wavelength of the light source is around 800 nm, and therefore 800
There is a strong demand for the development of a photoconductor having high sensitivity to long-wavelength light of around nm. Materials which meet this purpose are disclosed in JP-A-59-49544 and JP-A-59-59.
214034, JP 61-109056, JP 61-171771, JP 61-2.
17050, Japanese Patent Laid-Open No. 61-239248,
JP-A-62-67094, JP-A-62-1346
51, JP-A-62-275272, JP-A-63-198067, and JP-A-63-198068.
JP, JP-A-63-210942, JP, JP-A-63
Materials described in JP-A-218768, etc.
Various oxytitanium phthalocyanines each having a crystal type suitable as a material for an electrophotographic photoreceptor are known. However, there has been a further demand for an electrophotographic photoreceptor having high sensitivity to long-wavelength light and excellent other electric characteristics.

The present invention has been made to solve the above problems, and a first object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and high durability. The second object is high sensitivity, the residual potential is sufficiently low even when the film thickness is increased, the characteristic is small even after repeated use, and the electrophotographic photoreceptor has excellent durability. To provide. A third object is to provide a well-balanced electrophotographic photoreceptor having high sensitivity even at a long wavelength of about 800 nm and good chargeability, dark decay, residual potential and the like.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have found that a specific arylamine compound is suitable as a result of intensive research on organic low-molecular photoconductive compounds that can satisfy these objects. Came to. That is, the gist of the present invention is to provide the following general formula [I] on a conductive support.

[0009]

[Chemical 8]

(Wherein x ₁ and x ₂ are hydrogen atoms or a general formula [IIA] or [IIB])

[0011]

[Chemical 9]

[0012]

[Chemical 10] Represents a group represented by and x ₁ and x ₂ may be the same or different; Y is a compound represented by the general formula [III]

[0013]

Embedded image —O—A ¹ —O— [III]

Alternatively, the general formula [IV]

[0015]

Embedded image —A ² —O—A ³ — [IV]

Represents a group represented by the general formula [III]
In the above, A ¹ is an alkylene group which may have a substituent ,
Is an alkylene group which may have a substituent and a substituent
Represents a group to which an arylene group which may be present is bonded , and in the general formula [IV], A ² and A ³ each represent an alkylene group which may have a substituent, and A ² and A ³ are the same as each other. Or they may be different; R ¹ , R ² , R ³ , R
⁴ , R ³ ′ and R ⁴ ′ each represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituted amino group, which are mutually May be the same or different;
^{R 5, R 6, R 7} , R 8, R 9, R 10, R 11, R
¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each may have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a good heterocyclic group, which may be the same as or different from each other, or R ⁶ and R ⁷ , R ⁹ and R ¹⁰ , R
¹² and R ¹³ , R ¹⁵ and R ¹⁶ may be condensed to form a carbocyclic group or a heterocyclic group, provided that a pair of R ⁶ and R ⁷ , a pair of R ⁹ and R ¹⁰ , ^{When one of the} pair consisting of ¹² and R ¹³ and the pair consisting of R ¹⁵ and R ¹⁶ is a hydrogen atom or an alkyl group, the other is
It is an aryl group or a heterocyclic group. ) In an electrophotographic photoconductor characterized by having a photosensitive layer containing an arylamine compound represented by

[0017]

[0018]

Further, the present invention is characterized by further comprising a photosensitive layer containing an arylamine compound represented by the above-mentioned general formula [1] as a charge transporting material and an oxytitanium phthalocyanine as a charge generating material on a conductive support. It exists in the electrophotographic photoreceptor.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The electrophotographic photoreceptor of the present invention contains the arylamine compound represented by the general formula [I] in the photosensitive layer. In the general formula [I], x ₁ and x ₂ represent a hydrogen atom or a group represented by the general formulas [IIA] and [IIB]. x ₁ and X ₂ may be the same or different from each other. Y is a general formula [III]

[0021]

Embedded image —O—A ¹ —O— [III]

Alternatively, the general formula [IV]

[0023]

Embedded image represents a group represented by —A ² —O—A ³ — [IV]. In formula (III), A ¹ is a methylene group, an ethylene group, alkylene groups such as propylene group; and an alkylene group such as xylylene group; a phenylene group, biphenylene group, <br/> Ali alkarylene group such as a naphthylene group cycloalkylene groups such as cyclohexylene group; ants over <br/> alkylene group bonded groups represents a divalent hydrocarbon residue vinylene group, especially an alkylene group, Ali alkarylene group or an alkylene group and ants, preferably a group alkarylene groups attached. General formula (I
V], A ² and A ³ are each an alkylene group,
Ali alkarylene group, or represents an alkylene group and Ali alkarylene group attached groups, A ² and A ³ may be the same or different, they A ^1, groups A ² and A ³ is a halogen atom, It may have a substituent such as a hydroxyl group, a saturated or unsaturated hydrocarbon group (alkyl group, aryl group, etc.), an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group.

[0024] ^{R 1, R 2, R 3} , R 4, R 3 ' and R
⁴ 'are each a hydrogen atom; a chlorine atom, a bromine atom, a halogen atom such as iodine atom: methyl group, an ethyl group, an alkyl group such as propyl group; methoxy group, an ethoxy group, and propyl group alkoxy group; dimethylamino Groups such as dialkylamino groups, diphenylamino groups such as diarylamino groups, dibenzylamino groups such as diaralkylamino groups; diheterocyclic amino groups such as dipyridylamino groups, diallylamino groups, and substitution of the above amino groups Represents a substituted amino group such as a disubstituted amino group in which groups are combined, and these may be the same or different from each other, and particularly, a hydrogen atom,
A methyl group and a methoxy group are preferred. These alkyl group and alkoxy group may have a substituent, and as the substituent, a hydroxyl group; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a propyl group or a butyl group Alkyl group such as hexyl group; Alkoxy group such as methoxy group, ethoxy group, butoxy group; Allyl group; Aralkyl group such as benzyl group, naphthylmethyl group and phenethyl group; Aryloxy group such as phenoxy group and triloxy group; Benzyl group Arylalkoxy groups such as oxy group and phenethyloxy group; aryl groups such as phenyl group and naphthyl group; arylvinyl groups such as styryl group and naphthylvinyl group; dialkylamino groups such as dimethylamino group and diethylamino group; diphenylamino group, Diarylamino groups such as dinaphthylamino group; dibenzylamino group, diphe Chiruamino diaralkylamino groups such as; dipyridyl amino group, di heterocyclic amino groups such as Jichieniruamino group;
Examples include diallylamino group, and disubstituted amino groups in which the above-mentioned amino group substituents are combined.

R^Five, R⁶, R⁷, R⁸, R⁹, R^Ten, R
¹¹, R¹², R¹³, R¹⁴, R¹⁵And R ¹⁶Respectively water
Elementary atom; alkyl such as methyl, ethyl, propyl, etc.
Groups; phenyl groups, naphthyl groups, anthracenyl groups, etc.
Reel group; pyrrolyl group, thienyl group, furyl group, carba
Represents a heterocyclic group such as a zolyl group, which are the same as each other.
May also be different. Heterocyclic groups are especially aromatic
Heterocyclic groups are preferred. These alkyl groups, aryl
The group and the heterocyclic group may have a substituent,
The group is a hydroxyl group; chlorine atom, bromine atom, iodine atom
Halogen atom such as methyl group, ethyl group, propyl group,
Alkyl groups such as butyl and hexyl; methoxy and ether
Alkoxy group such as toxy group and butoxy group; allyl group;
Aralkyl groups such as benzyl, naphthylmethyl, phenethyl, etc.
Kill group; aryloxy such as phenoxy group and triloxy group
Si group; ants such as benzyloxy group and phenethyloxy group
Alkoxy group; aryl such as phenyl group and naphthyl group
Group; aryl vinyl such as styryl group and naphthyl vinyl group
Group; dial such as dimethylamino group and diethylamino group
Kiramino group; diphenylamino group, dinaphthylamino group
Groups such as diarylamino groups; dibenzylamino groups, dif
Diaralkylamino group such as phenethylamino group; dipyridy
Diheterocyclic amino such as ruamino and dithienylamino
A group; a diallylamino group, or a substituent of the above amino group
Examples thereof include a di-substituted amino group in combination.

Further, R ⁶ and R ⁷ , R ⁹ and R ¹⁰ , R ¹² and R
¹³ , R ¹⁵ and R ¹⁶ are condensed to form a carbocyclic group through a single bond, a methylene group, an ethylene group, a carbonyl group, a vinylidene group, an ethylenylene group or the like; a heterocycle containing an oxygen atom, a sulfur atom, a nitrogen atom or the like. It may form a ring group, and further, those rings may have a substituent, and as the substituent, a methyl group, an ethyl group, an alkyl group such as a propyl group; a phenyl group, a naphthyl group, An aryl group such as anthracenyl group;
Cyano group; alkoxycarbonyl group; aryloxycarbonyl group; nitro group; halogen atoms such as chlorine atom, bromine atom, iodine atom and the like. However, R ⁶ and R ⁷
The pair consisting of, R ⁹ and R ¹⁰ , the pair consisting of R ¹² and R ^13, and the pair consisting of R ¹⁵ and R ¹⁶ are each a hydrogen atom or an alkyl group, the other is: It is an aryl group or a heterocyclic group.

Y in the general formula [I] is represented by the general formula [II]
In the case of the group represented by I]^Five, R ⁶, R⁷, R⁸, R
⁹, R^Ten, R¹¹, R¹², R¹³, R¹⁴, R¹⁵And R
¹⁶Are a hydrogen atom and an alkyl which may have a substituent, respectively.
Kill group, aryl group which may have a substituent, or substituent
Represents a heterocyclic group which may have
Or they may be different, provided that R⁶And R⁷Consists of
Pair, R⁹And R^TenA pair consisting of R¹²And R¹³A pair consisting of R
¹⁵And R¹⁶Is a hydrogen atom, one of which is a hydrogen atom.
Or when it is an alkyl group, the other of the pair is aryl
A group or a heterocyclic group, or R⁶And R⁷, R
⁹And R^Ten, R¹²And R¹³, R¹⁵And R¹⁶Is the following general formula
The dotted line in [I '] and general formulas [IIA'] and [IIB ']
To form a condensed carbocyclic or heterocyclic group as shown in
And the rings may have a substituent.
X₁And x₂When is a hydrogen atom, R⁶And R⁷
A pair consisting of R⁹And R^TenAt least one of the pairs consisting of
The pairs may be fused to form carbocyclic or heterocyclic groups.
preferable.

[0028]

[Chemical 16]

[0029]

[Chemical 17]

[0030]

[Chemical 18] Typical examples of the arylamine compounds represented by the general formula [I] are shown below. However, since these representative examples are shown for the purpose of illustration, the arylamine compounds used in the present invention are not limited to these representative examples. It is not limited.

[0031]

[Chemical 19]

[0032]

[Chemical 20]

[0033]

[Chemical 21]

[0034]

[Chemical formula 22]

[0035]

[Chemical formula 23]

[0036]

[Chemical formula 24]

[0037]

[Chemical 25]

[0038]

[Chemical formula 26]

[0039]

[Chemical 27]

[0040]

[Chemical 28]

The arylamine compound represented by the above general formula [I] can be produced by a known method. For example, using a known arylamine compound as a raw material,
A known carbonyl introduction reaction is performed and then Wittig
It is a method of obtaining a target compound by carrying out a reaction. To explain this method in detail, firstly, (1) when x ₁ is the general formula [IIA] and x ₂ is H, as follows:

[0042]

[Chemical 29]

When R ⁸ = H, the general formula [VII] (wherein Y, R ¹ , R ² , R ³ , R ⁴ , R
^{3 ', R 4', R} 5, R 6, R 7, R 8, R 11, R 12,
And R ¹³ have the same meaning as in general formula [I]. In the presence of phosphorus oxychloride, an arylamine compound represented by the formula: N, N-dimethylformamide, N-
When reacted with a formylating agent such as methylformanilide, an aldehyde compound represented by the general formula [VIII] is obtained. The formylating agent may be used in a large excess to serve as the reaction solvent, but an inert solvent for the reaction such as O-dichlorobenzene or benzene may be used.

When R ⁸ ≠ H, the arylamine compound represented by the general formula [VII] is
Aluminum chloride, iron chloride, the presence of a Lewis acid and zinc chloride, nitrobenzene, dichloromethane, four in a solvent such as carbon tetrachloride, by reaction with an acid chloride represented by the general formula Cl-CO-R ^8, formula [ A ketone body represented by [VIII] is obtained.

Then, the obtained aldehyde or ketone represented by the general formula [VIII] and N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, benzene, toluene and the like are inert to the reaction. In a known organic solvent, the general formula [IX] (the general formula [I
X], R ⁹ and R ¹⁰ have the same meaning as in formula [I], and Q represents a halogen atom such as a chlorine atom or a bromine atom. ) Or a triphenylphosphine, or a halogen compound and a trialkoxyphosphorus compound (R ¹⁹ O) ₃ P (R
¹⁹ represents an alkyl group such as a methyl group and an ethyl group. )
10 to 2 with the Wittig reagent obtained by reacting with
By reacting at a temperature of 00 ° C, preferably 20 to 100 ° C in the presence of a known basic catalyst such as butyllithium, phenyllithium, sodium methoxide, sodium ethoxide, potassium t-butoxide, the compound of the general formula [X] A compound represented by At this time, either a cis isomer, a trans isomer, or a mixture of a cis isomer and a trans isomer is obtained. (In the present invention, the general formula [I] is
Represents either a cis form, a trans form, or a mixture of a cis form and a trans form. )

[0046]

[Chemical 30]

[0047]

[Chemical 31]

R¹⁴= H General formula [X] (where Y, R¹, R², R³, R^Four，
R³′, R^Four′, R^Five, R ⁶, R⁷, R⁸, R⁹，
R^Ten, R¹¹, R¹², R¹³, R¹⁴In the general formula [I]
Has the same meaning as. ) Arylamine
Compound in the presence of phosphorus oxychloride in N, N-dimethyl
Formyl such as formamide and N-methylformanilide
Aldehydes represented by the general formula [XI] when reacted with an agent
The body is obtained. Reaction solvent using a large excess of formylating agent
Can also serve as O-dichlorobenzene, benzene
It is also possible to use a solvent inert to the reaction such as Zen. R¹⁴When ≠ H

[0049]

[Chemical 32]

The arylamine compound represented by the general formula [X] is treated with a general formula Cl--CO--R in the presence of a Lewis acid such as aluminum chloride, iron chloride or zinc chloride in a solvent such as nitrobenzene, dichloromethane or carbon tetrachloride. By reacting with an acid chloride represented by ¹⁴ , a ketone body represented by the general formula [XI] is obtained. Then, the obtained aldehyde or ketone represented by the general formula [XI] and N, N
-Dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, benzene, toluene or the like in a known organic solvent inert to the reaction, represented by the general formula [XI
I] (in the general formula [XII], R ¹⁵ and R ¹⁶ have the same meaning as in the general formula [I], and Q represents a halogen atom such as chlorine atom or bromine atom). By reacting a halogen compound with triphenylphosphine or by reacting the halogen compound with a trialkoxyphosphorus compound (R ¹⁹ O) ₃ P (R ¹⁹ represents an alkyl group such as a methyl group or an ethyl group). The obtained Wittig reagent is mixed at 10 to 200 ° C., preferably 20 to 100.
Butyl lithium, phenyl lithium, sodium methoxide, sodium ethoxide, potassium t at a temperature of ℃
-By reacting in the presence of a known basic catalyst such as butoxide, a compound represented by the general formula [I] can be obtained.

[0051]

[Chemical 33]

When R ⁸ = H, the general formula [VII] (wherein Y, R ¹ , R ² , R ³ , R ⁴ , R
³ ′, R ⁴ ′, R ⁵ , R ⁶ , R ⁷ and R ⁸ are represented by the general formula [I]
Has the same meaning as in. In the presence of phosphorus oxychloride, an arylamine compound represented by
By reacting with a formylating agent such as dimethylformamide or N-methylformanilide to purify the mixture, the aldehyde compound represented by the general formula [XIV] can be obtained. The formylating agent may be used in a large excess to serve as the reaction solvent, but an inert solvent for the reaction such as O-dichlorobenzene or benzene may be used.

When R ⁸ ≠ H, the arylamine compound represented by the general formula [XIII] is
To purify the mixture by reacting it with an acid chloride represented by the general formula Cl-CO-R ⁸ in the presence of a Lewis acid such as aluminum chloride, iron chloride or zinc chloride in a solvent such as nitrobenzene, dichloromethane or carbon tetrachloride. According to the general formula [XI
A ketone body represented by V] is obtained. A known organic compound which is inactive in the reaction of the aldehyde or ketone represented by the general formula [XIV] with N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, benzene, toluene or the like. In a solvent, in the general formula [XV] (in the general formula [XV], R ⁹ and R ¹⁰ have the same meanings as in the general formula [I], and Q is
A halogen atom such as a chlorine atom or a bromine atom is shown. ) Or a triphenylphosphine or a halogen compound and a trialkoxyphosphorus compound (R ¹⁹ O) ₃ P (R ¹⁹ represents an alkyl group such as a methyl group or an ethyl group). And a Wittig reagent obtained by the reaction of 10 to 200 ° C., preferably 20 to 200 ° C.
The compound represented by the general formula [XVI] is obtained by reacting at a temperature of 100 ° C. in the presence of a known basic catalyst such as butyllithium, phenyllithium, sodium methoxide, sodium ethoxide, potassium t-butoxide. .

[0054]

[Chemical 34] In these reactions, in some cases, after completion of each step, or after completion of all steps, recrystallization purification, sublimation purification,
It is also possible to obtain a highly purified product by a known purification means such as column purification. The electrophotographic photoreceptor of the present invention has a photosensitive layer containing one or more arylamine compounds represented by the above general formula [I].

The arylamine compound represented by the general formula [I] exhibits excellent performance as an organic photoconductor. In particular, when it is used as a charge transport medium, it gives a photoreceptor having high sensitivity and excellent durability. Various forms of the photosensitive layer of the electrophotographic photosensitive member are known, and any of them may be used as the photosensitive layer of the electrophotographic photosensitive member of the present invention.

The photosensitive layer (photoconductive layer) is a layered type in which a charge generation layer and a charge transport layer are laminated in this order, or a laminate in which they are laminated in the opposite order. Further, a charge generation material (charge generation substance) is contained in a charge transport medium. Any structure such as a so-called dispersion type in which the particles of 1) are dispersed can be used. For example, a photosensitive layer in which an arylamine compound and a dye serving as a sensitizer or an electron-withdrawing compound is added to a binder as necessary, a charge-generating material (photoconductive particle) that generates a charge carrier with extremely high efficiency when absorbing light. ) And an arylamine compound in a binder, a photosensitive layer, a charge transport layer composed of an arylamine compound and a binder, and a charge generating material that generates a charge carrier with extremely high efficiency when absorbing light, or from this and a binder. And a charge generation layer that is laminated.

In these photosensitive layers, along with the arylamine compound represented by the general formula [I], other known arylamine compounds, hydrazone compounds, stilbene compounds having excellent performance as organic photoconductors, etc. May be mixed. Among them, in an electrophotographic photoreceptor having at least a photosensitive layer on a conductive substrate, an arylamine compound represented by the above general formula [I] and a pyrenehydrazone represented by the following general formula [V] in the photosensitive layer. An electrophotographic photosensitive member characterized by containing a system compound is preferable.

The electrophotographic photoconductor in which these specific two kinds of compounds are contained in this photosensitive layer has extremely high photosensitivity and shows a low residual potential, and even if it is repeatedly used, almost no residual potential is accumulated. In addition, it has excellent durability because it has very little fluctuation in charging property and sensitivity and extremely good stability, and can be used in a high-speed copying machine or printer without any problem.

[0059]

[Chemical 35]

In the general formula [V], R ¹⁷ represents an alkyl group, an allyl group, an aryl group or an aralkyl group, and the aryl group and the aralkyl group may have a substituent, and preferably have a substituent. The aryl group which may be present is particularly preferably a phenyl group and a naphthyl group. R ¹⁸
Represents an aryl group which may have a substituent, and a phenyl group and a naphthyl group are particularly preferable. Examples of the substituent here include an alkyl group, an allyl group, an alkoxy group, an aryloxy group and a dialkylamino group. Typical examples of the pyrene hydrazone compounds represented by the general formula [V] are shown below, but these representative examples are shown for the purpose of illustration, and the pyrene hydrazone compounds used in the present invention are limited to these representative examples. It is not something that will be done.

[0061]

[Table 1] B-1 1-pyrenecarbaldehyde methylphenyl
Hydrazone B-2 1-pyrenecarbaldehyde ethylphenyl
Hydrazone B-3 1-pyrenecarbaldehyde allylphenyl
Hydrazone B-4 1-pyrenecarbaldehyde diphenyl hydrazone B-5 1-pyrenecarbaldehyde benzylphenyl hydrazone B-6 1-pyrenecarbaldehyde-phenyl-1-naphthyl hydrazone B-7 1-pyrenecarbaldehyde-phenyl-2- Naphthyl hydrazone B-8 1-pyrene carbaldehyde-phenyl 4-methoxyphenyl hydrazone B-9 1-pyrene carbaldehyde-phenylphenoxyphenyl hydrazone B-10 1-pyrene carbaldehyde-phenyl-3-methylphenyl hydrazone B-11 1 -Pyrenecarbaldehyde-phenyl-4-methylphenyl hydrazone B-12 1-pyrenecarbaldehyde-phenyl-4-methoxyphenyl hydrazone B-13 1-pyrenecarbaldehyde-phenyl-4-diethylamino Eniruhidorazon B-14 1-pyrene-carbaldehyde - di - (2-naphthyl) hydrazone

The compounding ratio of the compound represented by the general formula [I] or the general formula [V] is, by weight, usually 95: 5 to 2 or 2.
It is in the range of 0 to 80, but 90 for higher effect
A range of 10 to 40 to 60 is preferred. The following are representative examples of particularly preferable combinations of the arylamine compound represented by the general formula [I] and the pyrenehydrazone compound represented by the general formula [V]. These representative examples are shown for the purpose of illustration. Therefore, the arylamine compounds and pyrenehydrazone compounds used in the present invention are not limited to these representative examples. Representative Examples Representative Examples of the Arylamine Compounds The Pyrenehydrazone Compounds

[0063]

[Table 2]   (1) A-1 B-4   (2) A-1 B-6   (3) A-1 B-7   (4) A-1 B-8   (5) A-1 B-10   (6) A-1 B-11   (7) A-1 B-12   (8) A-2 B-4   (9) A-2 B-6   (10) A-2 B-7   (11) A-2 B-8   (12) A-2 B-10   (13) A-2 B-11   (14) A-2 B-12   (15) A-3 B-4   (16) A-3 B-6   (17) A-3 B-7   (18) A-3 B-8   (19) A-3 B-10   (20) A-3 B-11   (21) A-3 B-12   (22) A-4 B-4   (23) A-4 B-6   (24) A-4 B-7   (25) A-4 B-8

[0064]

[Table 3]   (26) A-4 B-10   (27) A-4 B-11   (28) A-4 B-12   (29) A-5 B-4   (30) A-5 B-6   (31) A-5 B-7   (32) A-5 B-8   (33) A-5 B-10   (34) A-5 B-11   (35) A-5 B-12   (36) A-6 B-4   (37) A-6 B-6   (38) A-6 B-7   (39) A-6 B-8   (40) A-6 B-10   (41) A-6 B-11   (42) A-6 B-12   (43) A-29 B-4   (44) A-29 B-6   (45) A-29 B-7   (46) A-29 B-8   (47) A-29 B-10   (48) A-29 B-11   (49) A-29 B-12   (50) A-30 B-4   (51) A-30 B-6   (52) A-30 B-7

[0065]

[Table 4]   (53) A-30 B-8   (54) A-30 B-10   (55) A-30 B-11   (56) A-30 B-12   (57) A-31 B-4   (58) A-31 B-6   (59) A-31 B-7   (60) A-31 B-8   (61) A-31 B-10   (62) A-31 B-11   (63) A-31 B-12   (64) A-35 B-4   (65) A-35 B-6   (66) A-35 B-7   (67) A-35 B-8   (68) A-35 B-10   (69) A-35 B-11   (70) A-35 B-12   (71) A-36 B-4   (72) A-36 B-6   (73) A-36 B-7   (74) A-36 B-8   (75) A-36 B-10   (76) A-36 B-11   (77) A-36 B-12   (78) A-37 B-4   (79) A-37 B-6

[0066]

[Table 5]   (80) A-37 B-7   (81) A-37 B-8   (82) A-37 B-10   (83) A-37 B-11   (84) A-37 B-12   (85) A-41 B-4   (86) A-41 B-6   (87) A-41 B-7   (88) A-41 B-8   (89) A-41 B-10   (90) A-41 B-11   (91) A-41 B-12   (92) A-42 B-4   (93) A-42 B-6   (94) A-42 B-7   (95) A-42 B-8   (96) A-42 B-10   (97) A-42 B-11   (98) A-42 B-12   (99) A-43 B-4   (100) A-43 B-6   (101) A-43 B-7   (102) A-43 B-8   (103) A-43 B-10   (104) A-43 B-11   (105) A-43 B-12   (106) A-55 B-4

[0067]

[Table 6]   (107) A-55 B-6   (108) A-55 B-7   (109) A-55 B-8   (110) A-55 B-10   (111) A-55 B-11   (112) A-55 B-12   (113) A-61 B-4   (114) A-61 B-6   (115) A-61 B-7   (116) A-61 B-8   (117) A-61 B-10   (118) A-61 B-11   (119) A-61 B-12

In the present invention, when the arylamine compound represented by the above general formula [I] is used in a charge transport layer of a photosensitive layer comprising two layers of a charge generation layer and a charge transport layer (charge transfer layer), In particular, it is possible to obtain a photoreceptor having a high sensitivity and a small residual potential, and having little variation in surface potential, a decrease in sensitivity, accumulation of residual potential, and the like when repeatedly used, and having excellent durability.

Specifically, usually, a charge generating material is directly vapor-deposited or applied as a dispersion liquid with a binder to form a charge generating layer, and an organic solvent solution containing the arylamine compound is cast thereon, or Alternatively, the charge transporting layer containing the charge transporting material containing the arylamine compound represented by the above general formula [I] is prepared by dissolving the arylamine compound with a binder and coating the dispersion. Although it is a laminated type photoreceptor, the order of laminating the charge generation layer and the charge transport layer may be reversed.

Further, it may be a single-layer type photoreceptor in which the charge generating material and the charge transporting material are dispersed and dissolved in a binder and applied on a conductive support. As the charge generation material, selenium, selenium-tellurium alloy, selenium-arsenic alloy, cadmium sulfide, inorganic photoconductive particles such as amorphous silicon; metal-free phthalocyanine, metal-containing phthalocyanine, perinone pigment, thioindigo, quinacridone, perylene pigment, Examples include organic photoconductive particles such as anthraquinone pigments, azo pigments, bisazo pigments, trisazo pigments, tetrakis azo pigments, and cyanine pigments.

Further, various organic pigments and dyes such as polycyclic quinone, pyrylium salt, thiopyrylium salt, indigo, anthanthrone and pyrantrone can be used. Among them, metal-free phthalocyanine, copper indium chloride, gallium chloride, tin,
Metals such as oxytitanium, zinc, vanadium, or
Azo pigments such as phthalocyanines coordinated with their oxides and chlorides, monoazo, bisazo, trisazo and polyazos are preferable.

Among them, a combination of a metal-containing phthalocyanine and an arylamine compound represented by the above-mentioned general formula [I] gives a photoreceptor having improved sensitivity to laser light, and particularly, at least on a conductive support, In an electrophotographic photoreceptor having a photosensitive layer containing a charge generating material and a charge transporting material, the charge generating material has a main diffraction at a black angle (2θ ± 0.2 °) of 27.3 ° in an X-ray diffraction spectrum. It contains oxytitanium phthalocyanine exhibiting a peak, and as the charge transport material, the compound represented by the general formula [I]
An electrophotographic photoreceptor containing an arylamine compound represented by

The electrophotographic photosensitive member thus obtained has a high sensitivity, a low residual potential and a high charging property, and the fluctuation due to repetition is small, and in particular, the charging stability which affects the image density is good. Therefore, it can be used as a highly durable photoreceptor. Further, since it has a high sensitivity in the region of 750 to 850 nm, it is particularly suitable for a photoconductor for a semiconductor laser printer.

Oxytitanium phthalocyanine used as the charge generating material has a main diffraction peak at 27.3 ° of the black angle (2θ ± 0.2 °) in its X-ray diffraction spectrum. The above-mentioned “main diffraction peak” refers to the peak with the highest (highest) intensity in the X-ray diffraction spectrum. The powder X-ray spectrum of the oxytitanium phthalocyanine used has a black angle (2
The main peak is the diffraction peak at 27.3 °, but there are various variations depending on the detailed conditions, except for the peak intensity at 27.3 °. Of 50% or less is preferable in terms of charging property, sensitivity and the like as an electrophotographic photoreceptor.

The method for producing the oxytitanium phthalocyanine is not particularly limited, but for example, it is produced by the following method. A method for producing a [II] type crystal described in Production Example 1 of JP-A-62-67094. That is, orthophthalodinitrile and a halide of titanium are heated and reacted in an inert organic solvent, and then hydrolyzed. Direct Various crystal forms of oxytitanium phthalocyanine, an organic acid solvent, sulfuric acid or the formula R-SO ₃ H (wherein, R
Represents an aliphatic or aromatic residue which may have a substituent. ) Or a sulfonated compound represented by the formula (1) or, if necessary, a mixed solvent of an insoluble organic solvent and water. If desired, it is dissolved in concentrated sulfuric acid and then released into ice water, or after being amorphized by a known method such as a mechanical grinding method such as a paint shaker, a ball mill, a sand grind mill or the like, it is heat treated with the above sulfonate or water. Heat treatment with a mixed solvent of an insoluble organic solvent and water. In the case of the treatment with the above-mentioned sulfonated product, it can be produced by using a mechanical grinding method such as a paint shaker, a ball mill and a sand grind mill instead of the heat treatment.

The oxytitanium phthalocyanine particles showing a main diffraction peak at a black angle (2θ ± 0.2 °) of 27.3 ° in the X-ray diffraction spectrum are a binder polymer and, if necessary, other organic photoconductive compound, dye and the like. The compound is dissolved or dispersed in a solvent together with the electron-withdrawing compound, and the coating solution thus obtained is applied and dried to obtain a charge generation layer. For example, oxytitanium phthalocyanine showing a main diffraction peak at the black angle (2θ ± 0.2 °) 27.3 ° of the X-ray diffraction spectrum and the black angle (2θ ± 0.2 °) 9.3 of the X-ray diffraction spectrum 9.3. °, 13.2
Using oxytitanium phthalocyanine showing major diffraction peaks at °, 26.2 ° and 27.1 °,
Alternatively, the black angle (2θ ±
Oxytitanium phthalocyanine showing a main diffraction peak at 0.2 °) 27.3 ° and a black angle (2θ ± 0.2 °) of X-ray diffraction spectrum 8.5 °, 12.2 °, 1
It is preferable to use dichlorotin phthalocyanine which shows major diffraction peaks at 3.8 °, 16.9 °, 22.4 °, 28.4 ° and 30.1 °.

Examples of dyes optionally added in the present invention include triphenylmethane dyes such as methyl violet, brilliant green and crystal violet, and thiazine dyes such as methylene blue.
Examples thereof include quinone dyes such as quinizarin, cyanine dyes, pyrylium salts, thiabilylium salts, and benzopyrylium salts. Examples of the electron-withdrawing compound that forms a charge transfer complex with an arylamine compound include, for example, chloranil, 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, and 2 -Quinones such as chloroanthraquinone and phenanthrenequinone; aldehydes such as 4-nitrobenzaldehyde; 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 2,4,7-
Ketones such as trinitrofluorenone, 2,4,5,7-tetranitrofluorenone and 3,3 ′, 5,5′-tetranitrobenzophenone; acid anhydrides such as phthalic anhydride and 4-chloronaphthalic anhydride; Cyano compounds such as tetracyanoethylene, terephthalalmalononitrile, 9-anthrylmethylidene malononitrile, 4-nitrobenzalmalononitrile, 4- (p-nitrobenzoyloxy) benzalmalononitrile; 3-benzalphthalide, 3- (Α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,
Examples thereof include electron-withdrawing compounds such as phthalides such as 5,6,7-tetrachlorophthalide.

The charge generating layer in the laminated type photosensitive layer contains fine particles of these substances, such as polyester resin, polyvinyl acetate, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional,
It may be used in a dispersion layer in the form of being bound with various binder resins such as polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, cellulose ester and cellulose ether. Further, examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinyl alcohol and ethyl vinyl ether, polyamide, and silicon resin. In this case, the charge generation material (charge generation substance) is used in an amount of usually 20 to 2000 parts by weight, preferably 30 to 500 parts by weight, more preferably 33 to 500 parts by weight, based on 100 parts by weight of the binder resin. The thickness of the charge generation layer is usually 0.05 to 5 μm, preferably 0.1 μm.
To 2 μm, more preferably 0.15 μm to 0.8 μm
m is preferred. Further, the charge generation layer may contain various additives such as a leveling agent, an antioxidant and a sensitizer for improving the coating property, if necessary. Furthermore, the charge generation layer may be a vapor deposition film of the above charge generation material.

In the case of the dispersion type photosensitive layer, the particle size of the charge generating material needs to be sufficiently small, and it is preferably 1 μm or less, more preferably 0.5 μm or less. The amount of the charge generating material dispersed in the photosensitive layer is, for example, 0.5 to 5
If it is in the range of 0% by weight but too small, sufficient sensitivity cannot be obtained, and if it is too large, there are adverse effects such as a decrease in charging property and a decrease in sensitivity. More preferably, it is used in the range of 1-20% by weight. .

The thickness of the dispersion type photosensitive layer is usually 5 to 50 μm,
It is more preferably used in the range of 10 to 45 μm. Also in this case, known plasticizers for improving film-forming properties, flexibility, mechanical strength, etc., additives for suppressing residual potential, dispersion aids for improving dispersion stability, and coating properties are used. Leveling agents and surface active agents such as silicone oil, fluorine-based oil and other additives may be added for improvement.

Further, the photosensitive layer of the electrophotographic photosensitive member of the present invention may contain a well-known plasticizer in order to improve film-forming property, flexibility and mechanical strength. Therefore, examples of the plasticizer added to the coating solution include phthalic acid esters, phosphoric acid esters, epoxy compounds, chlorinated paraffins, chlorinated fatty acid esters, and aromatic compounds such as methylnaphthalene. When the arylamine compound is used as the charge transport material in the charge transport layer, the coating solution may have the above composition, but the photoconductive particles, dye pigment, electron withdrawing compound, etc. may be removed or added in a small amount. Good. In this case, as the charge generation layer, a coating liquid obtained by dissolving or dispersing in the solvent such as the above-mentioned photoconductive particles and optionally a binder polymer or other organic photoconductive substance, dye pigment, electron-withdrawing compound is applied. Examples thereof include a dried thin layer or a layer formed by film-forming the photoconductive particles.

The photoreceptor thus formed may also have an improved electrical property and mechanical property such as a barrier layer, an intermediate layer such as an adhesive layer and a blocking layer, a transparent insulating layer, or a protective layer, if necessary. It goes without saying that it may have a layer for. As the conductive support on which the photosensitive layer is formed, any of those known in electrophotographic photoreceptors can be used. Specifically, for example, aluminum, stainless steel, copper, a drum made of a metal material such as nickel, a sheet or a laminate of these metal foils, a deposit, or aluminum, copper, palladium on the surface,
Examples thereof include a polyester film provided with a conductive layer such as tin oxide and indium oxide, and an insulating support such as paper. Further, there may be mentioned plastic films, plastic drums, papers, paper tubes, etc. which have been subjected to a conductive treatment by coating a conductive material such as metal powder, carbon black, copper iodide, or a polymer electrolyte with a suitable binder. In addition, examples include conductive plastic sheets and drums containing conductive materials such as metal powder, carbon black, and carbon fibers. Further, a plastic film or a belt that has been subjected to a conductive treatment with a conductive metal oxide such as tin oxide or indium oxide can be given.

Of these, an endless pipe made of a metal such as aluminum is a preferable support. As the barrier layer and the intermediate layer, for example, an anodized aluminum film, an aluminum oxide, an inorganic layer such as aluminum hydroxide, polyvinyl alcohol, casein, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, polyamide, Etc. are used.

In the electrophotographic photoreceptor of the present invention, the arylamine compound represented by the above general formula [I] is dissolved in a suitable solvent together with a binder according to a conventional method. A coating solution obtained by adding a well-known additive such as an infectious agent, an electron-withdrawing compound, another charge-transporting material, or a plasticizer or a pigment is coated on a conductive support and dried, and usually several times. μ to several tens μ, preferably 1
It can be produced by forming a photosensitive layer having a film thickness of 0 to 45 μm, particularly preferably 27 μm or more. In the case of a photosensitive layer consisting of a charge generation layer and a charge transport layer,
It can be produced by applying the coating liquid on the charge generation layer or forming the charge generation layer on the charge transport layer obtained by applying the coating liquid.

As the solvent for preparing the coating solution, ethers such as tetrahydrofuran, 1,4-dioxane, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide, acetonitrile, N-methylpyrrolidone,
Aprotic polar solvents such as dimethyl sulfoxide; esters such as ethyl acetate, methyl formate and methyl cellosolve acetate; solvents that dissolve arylamine compounds such as chlorinated hydrocarbons such as dichloroethane and chloroform. Of course, it is necessary to select one that dissolves the binder from these.

As the binder resin used in the charge transport layer in the case of the laminated type photosensitive layer or the binder resin used as the matrix in the case of the dispersed type photosensitive layer,
Good compatibility with the charge transport material, the charge transport material is not crystallized after forming a coating film, or a polymer which does not undergo phase separation, for example, styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, Polymers and copolymers of vinyl compounds such as butadiene, polyvinyl acetal, polycarbonate, polyester, polyester carbonate, polysulfone, polyimide,
Examples thereof include various polymers such as polyphenylene oxide, polyurethane, cellulose ester, cellulose ether, phenoxy resin, silicon resin and epoxy resin, and partially cross-linked cured products thereof can also be used. The amount of the binder used is usually 0.5 with respect to the arylamine compound.
-30 times by weight, preferably 0.7 to 10 times by weight.

In the photosensitive layer containing the arylamine compound represented by the general formula [I] and the pyrenehydrazone compound represented by the general formula [V], the charge transport layer in the laminated type photosensitive layer is basically the same. Specifically, it is composed of an arylamine compound represented by the general formula [I] and a pyrenehydrazone compound represented by the general formula [V] together with a binder resin. The charge generating material described above is dispersed in a matrix containing a compound represented by the general formula [I] or the general formula [V] as a main component.

In this case, the amount of the binder resin used is 0.5 to 3.3 times by weight, preferably 0.5 to 3.3 times the total amount of the compound represented by the general formula [I] and the compound represented by the general formula [V]. It is used in the range of 0.66 to 2.5 times by weight.
Further, the compound represented by the general formula [I] is preferably used in an amount of more than 20% by weight in the charge transport layer in the case of the laminated type or in the photosensitive layer in the case of the dispersed type, in order to obtain a higher effect. More preferably in the range of 25 to 45 weight percent.

In the case of the laminated type photosensitive layer, the charge transport layer may optionally contain various additives such as an antioxidant and a sensitizer, and other charge transport materials. The thickness of the charge transport layer is usually 10 to 60 μm, preferably 10 to 45 μm,
More preferably, it is used with a thickness of 27 to 40 μm. As the outermost surface layer, a conventionally known overcoat layer mainly composed of a thermoplastic or thermosetting polymer may be provided. Usually, the charge transfer layer is formed on the charge generation layer, but the reverse is also possible. As a method for molding each layer, a known method such as sequentially coating a coating solution obtained by dissolving or dispersing a substance contained in the layer in a solvent can be applied.
In addition to the above, various additives for improving the mechanical strength and durability of the coating film can be used in the charge transport layer.

Examples of such additives include well-known plasticizers, various stabilizers, fluidity imparting agents, crosslinking agents and the like. Examples of the coating method of the photosensitive layer include a spray coating method, a spiral coating method, a ring coating method and a dip coating method. Spray coating methods include air spray, airless spray, electrostatic air spray, electrostatic airless spray, rotary atomizing electrostatic spray, hot spray, hot airless spray, etc. Degree,
Considering the adhesion efficiency and the like, in the rotary atomization type electrostatic sprayer, the conveying method disclosed in the republication No. 1-805198 is repeated, that is, the cylindrical work is continuously rotated with no gap in its axial direction. By transporting the electrophotographic photosensitive member, it is possible to obtain an electrophotographic photosensitive member having high adhesion efficiency and excellent film thickness uniformity.

The spiral coating method is described in JP-A-52-
A method using a liquid injection coating machine or a curtain coating machine disclosed in Japanese Patent No. 119651, Japanese Patent Laid-Open No. 231966/1989.
Japanese Patent Laid-Open No. 3-193161 discloses a method using a multi-nozzle body for continuously ejecting paint in a streak pattern from a minute opening.

The dip coating method will be described below. An arylamine compound represented by the above general formula [I],
Suitable total solids concentration is 25 using binder, solvent, etc.
% Or more and more preferably 40% or less, and the viscosity is usually 50 centipoises to 300 centipoises or less, preferably 100 centipoises to 200 centipoises or less, to prepare a coating liquid for forming a charge transport layer. Here, the viscosity of the coating solution is substantially determined by the type of binder polymer and its molecular weight, but if the molecular weight is too low, the mechanical strength of the polymer itself will decrease and the binder polymer will have a molecular weight that does not impair it. Is preferably used. The charge transport layer is formed by the dip coating method using the coating liquid prepared as described above.

After that, the coating film is dried, and the drying temperature time may be adjusted so that necessary and sufficient drying is performed. The drying temperature is usually 100 to 250 ° C., preferably 110 to 17
0 ° C., more preferably 120 to 140 ° C. As a drying method, a hot air dryer, a steam dryer, an infrared dryer, a far infrared dryer or the like can be used.

[0094]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following production examples and examples as long as the gist thereof is not exceeded. In the examples, “part” means “part by weight”.

(Production Example 1)

[Chemical 36]

10 g of N, N-dimethylformamide 1
Dissolve in 00 ml, then phosphorus oxychloride 4.2m
1 was added, and then the mixture was reacted at 65 ° C. for 5 hours. After cooling, the reaction solution was discharged into 200 g of ice water, hydrolyzed with sodium hydroxide, and then subjected to extraction, concentration and purification treatment by a conventional method to give a yellow solid bisformyl compound 8 represented by the following structural formula. 0.5 g was obtained.

[0097]

[Chemical 37]

(Production Example 2) 2.0 g of the bisformyl compound synthesized in Production Example 1 and 1.6 g of diethylphenylmethylphosphonate were dissolved in 20 ml of THF, and the mixture was mixed at 10 ° C. ± 5.
At ° C, 0.95 g of potassium-tert-butoxide was added in small portions. Then, the mixture was stirred for 1 hour at room temperature. After cooling down,
The reaction solution is released into 20 g of ice water, and then extracted by a conventional method.
By concentrating and purifying, 1.7 g of pale yellow crystals (melting point: 115 to 118 ° C.) were obtained. This compound was identified as No. 1 by the following elemental analysis value and infrared absorption spectrum. It was found to be an arylamine compound represented by the structural formula of A-1. (Elemental analysis value) As C ₉₃ H ₇₀ N ₂ O ₂

[0099]

[Table 7] C% H% N% Measured value 89.53 5.66 2.25 Measured value 89.25 5.93 2.13 (Mass spectrometric measurement result) As C ₉₃ H ₇₀ N ₂ O ₂ Mw = 1248 Mw ⁺ = 1248

(Production Example 3) 2.0 g of the bisformyl compound synthesized in Production Example 1 and 1.2 g of diethylphenylmethylphosphonate were dissolved in 20 ml of THF, and the mixture was mixed at 10 ° C. ± 5.
At ° C, 0.95 g of potassium-tert-butoxide was added in small portions. Then, the mixture was stirred for 1 hour at room temperature. After cooling down,
The reaction solution is released into 20 g of ice water, and then extracted by a conventional method.
By concentrating and purifying, 1.5 g of pale yellow crystals (melting point: 112-115 ° C.) were obtained. According to the following elemental analysis values and infrared absorption spectrum (FIG. 1), this compound was identified as No. It was found to be an arylamine compound represented by the structural formula of A-2. (Elemental analysis value) As C ₈₁ H ₆₂ O ₂ N ₂

[0101]

[Table 8] C% H% N% Measured value 88.82 5.70 2.56 Measured value 88.59 5.83 2.51 (mass spectrometry measurement result) As C ₈₁ H ₆₂ O ₂ N ₂ Mw = 1095 Mw ⁺ = 1095

(Example 1) In the X-ray diffraction spectrum, black angle (2θ ± 0.2 °) 9.3 °, 10.6
°, 13.2 °, 15.1 °, 15.7 °, 16.1
Titanium oxyphthalocyanine pigment 1.0 showing strong diffraction peaks at 2 °, 20.8 °, 23.3 ° and 27.1 °
Parts to 14 parts of dimethoxyethane and dispersed with a sand grinder, then 14 parts of dimethoxyethane and 4-part
Methoxy-4-methylpentanone-2 (Mitsubishi Chemical Corporation)
(Manufactured by the company) and diluted with 14 parts, and further 0.5 parts by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo KK, trade name Denka Butyral # 6000-C) and phenoxy resin (manufactured by Union Carbide Co., Ltd., Trade name: UCAR (registered trademark) PKHH) 0.5 parts dimethoxyethane 6 parts, 4-
Mixing was performed with a liquid dissolved in a mixed solvent of 6 parts of methoxy-4-methylpentanone-2 to obtain a dispersion liquid. This dispersion is 7
The amino vapor deposition layer vapor-deposited on a polyester film having a thickness of 5 μm was coated with a wire bar so that the weight after drying was 0.4 g / m ² , and then dried to form a charge generation layer. 70 parts of the arylamine compound prepared in Preparation Example 3 and a polycarbonate resin shown below

[0103]

[Chemical 38]

A coating solution prepared by dissolving 100 parts of a mixed solvent of 585 parts of tetrahydrofuran and 315 parts of dioxane was applied and dried to form a charge transport layer having a film thickness of 17 μm.
The sensitivity, that is, the half-exposure amount was measured by the electrophotographic photosensitive member having the photosensitive layer composed of two layers thus obtained, and it was 0.46 μJ / cm ² . The half-exposure amount was obtained by first negatively charging the photoconductor in the dark with a corona current of 50 μA, and then passing white light of 20 lux through an interference filter to obtain light of 780 nm (exposure energy 10 μm).
W / cm ² ) and the surface potential is -450 V to -2.
It was determined by measuring the exposure dose required to attenuate to 25V. Further, the surface potential when the exposure time was set to 9.9 seconds was measured as a residual potential and found to be -6V. This operation was repeated 2000 times, but no increase in residual potential was observed.

Example 2 Instead of the titanium oxyphthalocyanine pigment used in Example 1, a black angle (2θ ± 0.2 °) of 9.5 was measured in an X-ray diffraction spectrum.
When a half-exposure amount was measured by exposing a photoconductor prepared in the same manner as in Example 1 except that a titanium oxyphthalocyanine pigment showing strong diffraction peaks at °, 27.1 ° and 27.3 ° was used and exposed to light of 780 nm. , 0.12 μJ / cm
² and the residual potential was -16V. (Example 3) A photoreceptor prepared in the same manner as in Example 1 was exposed to white light except that a naphthalic acid-based bisazo pigment represented by the following structural formula was used instead of the phthalocyanine-based pigment used in Example 1. When the half exposure was measured,
It was 0.53 lux · sec and the residual potential was −1V.

[0106]

[Chemical Formula 39]

Example 4 A photoconductor prepared in the same manner as in Example 1 except that a naphthalic acid-based bisazo pigment represented by the following structural formula was used in place of the phthalocyanine-based pigment used in Example 1 was subjected to white light. It was 0.67 lux.sec and the residual potential was -2V when the half exposure amount was measured.

[0108]

[Chemical 40]

(Examples 5 to 12) Instead of the arylamine compound used in Example 1, an arylamine compound shown in Table 1 below, which was synthesized in the same manner as in Production Example 3, was used. Table 1 shows the sensitivity and residual potential of the electrophotographic photosensitive member prepared in the same manner as in.

[0110]

[Table 9] Table 1 Example Example Compound No. Sensitivity (μJ / cm ² ) Residual potential (V) 5 A-1 0.48-10 6 A-3 0.46-7 7 A-10 0.70-12 8 A-14 0.80-20 9 A -27 0.85 -25 10 A-30 0.56 -8 11 A-58 0.65 -24 12 A-62 0.62 -15

Examples 13 to 20 Example 2 was repeated except that the arylamine compound shown in Table 2 below was synthesized in the same manner as in Production Example 3 instead of the arylamine compound used in Example 1. Table 2 shows the sensitivity and residual potential of the electrophotographic photosensitive member prepared in the same manner as in.

[0112]

Table 10 Table 2 Example Example compound No. Sensitivity (μJ / cm ² ) Residual potential (V) 13 A-1 0.13-25 14 A-3 0.12-17 15 A-5 0.15-20 16 A-10 0.23-20 17 A -13 0.20 -15 18 A-25 0.40 -50 19 A-41 0.16 -25 20 A-54 0.18 -30

(Examples 21 to 28) Examples 21 to 28 were replaced with the arylamine hydrazone compounds shown in Table 3 below, which were synthesized in the same manner as in Production Example 3 in place of the arylamine compounds used in Example 1. Table 3 shows the sensitivity and residual potential of the electrophotographic photosensitive member prepared in the same manner as in No. 3.

[0114]

[Table 11]                               Table 3     Example Exemplified compound No. Sensitivity (lux · sec) Residual potential (V)     21 A-1 0.53 -1     22 A-3 0.53 -2     23 A-9 0.55 -1     24 A-11 0.63 -4     25 A-14 0.80-10     26 A-18 0.57 -3     27 A-32 0.57 -5     28 A-36 0.60 -3

Comparative Example 1 An electrophotographic photosensitive member was obtained in the same manner as in Example 1 except that Comparative Compound 1 shown below was used instead of the arylamine compound used in Example 1. Comparative compound 1

[0116]

[Chemical 41]

Then, the sensitivity and the residual potential were measured in the same manner as in Example 1. The results are shown in Table 4 together with the measurement results for the photoconductor of Example 1. Comparative Example 2 A photoconductor was prepared in the same manner as in Comparative Example 1 except that Comparative Compound 2 shown below was used instead of Comparative Compound 1 used in Comparative Example 1, and the sensitivity and residual potential were measured. The results are shown in Table 4. Comparative compound 2

[0118]

[Chemical 42]

Comparative Example 3 A photoconductor was prepared in the same manner as in Comparative Example 1 except that Comparative Compound 3 shown below was used in place of Comparative Compound 1 used in Comparative Example 1, and the sensitivity and residual potential were measured. . The results are shown in Table 4.

Comparative compound 3

[0121]

[Chemical 43]

Comparative Example 4 A photoconductor was prepared in the same manner as in Comparative Example 1 except that Comparative Compound 4 shown below was used in place of Comparative Compound 1 used in Comparative Example 1, and the sensitivity and residual potential were measured. . The results are shown in Table 4. Comparative compound 4

[0123]

[Chemical 44]

[0124]

[Table 12] Table 4 Example Sensitivity (μJ / cm ² ) Residual potential (V) Comparative Example 1 0.60 −27 Comparative Example 2 0.59 −12 Comparative Example 3 0.59 −11 Comparative Example 4 0.51 -15 Example 1 0.46 -6

From Table 4, it is apparent that the compound of Example 1 shows superior values in both sensitivity and residual potential as compared with the compounds of Comparative Examples 1 to 4.

The electrophotographic photoreceptor of the present invention has a very high sensitivity and a small residual potential which causes fog.
In particular, since it has little light fatigue, it has characteristics that accumulation of residual potential due to repeated use, variation of surface potential and sensitivity are small, and excellent durability.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of an arylamine compound obtained in Production Example 3.

Continuation of front page (56) Reference JP-A-58-159536 (JP, A) JP-A-7-140685 (JP, A) JP-A-6-273950 (JP, A) JP-A-6-11854 (JP , A) JP 5-165239 (JP, A) JP 4-356052 (JP, A) JP 4-290851 (JP, A) JP 4-253065 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 5/00

Claims (10)

(57) [Claims] 1. On a conductive support, the following general formula [I]: (In the formula, x ₁ and x ₂ are hydrogen atoms, or a general formula [IIA] or [IIB]) [Chemical 3] Represents a group represented by and x ₁ and x ₂ may be the same or different from each other; Y is represented by the general formula [III] -O-A ¹ -O- [III] or the general formula [IV] Embedded image represents a group represented by —A ² —O—A ³ — [IV], and in the general formula [III], A ¹ has an alkylene group which may have a substituent or has a substituent. Shi
Optionally have an alkylene group and a substituent
Represents a group to which an arylene group is bonded , in the general formula [IV],
A ² and A ³ each represent an alkylene group which may have a substituent, and A ² and A ³ may be the same or different from each other; R ¹ , R ² , R ³ , R ⁴ and R ³ ′ And R ⁴ ′ each represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituted amino group, which are the same or different from each other. ^May be; R ⁵ , R ⁶ , R ⁷ , R
⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁵ and R ¹⁶ each represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. May be the same or different from each other, or R
⁶ and R ⁷ , R ⁹ and R ¹⁰ , R ¹² and R ¹³ , R ¹⁵ and R
¹⁶ may be condensed to form a carbocyclic group or a heterocyclic group, provided that a pair consisting of R ⁶ and R ⁷ , a pair consisting of R ⁹ and R ¹⁰ , a pair consisting of R ¹² and R ¹³ , ¹⁵ and R ¹⁶
When one of each pair is a hydrogen atom or an alkyl group, the other pair is an aryl group or a heterocyclic group. And an electrophotographic photoreceptor containing a photosensitive layer containing an arylamine compound. 2. A photosensitive layer comprising, on a conductive support, an arylamine compound represented by the general formula [I] as a charge transporting material and oxytitanium phthalocyanine as a charge generating material. The electrophotographic photoreceptor according to claim 1. 3. The Y in the general formula [I] is a group represented by the general formula [III].
Alternatively , the electrophotographic photoreceptor according to claim 2 . 4. The method of claim 1, characterized in that Y in the general formula [I] is a group represented by the general formula [IV] The
Is the electrophotographic photoreceptor according to claim 2 . 5. Y in the general formula [I] is a group represented by the general formula [III], and R ⁵ , R ⁶ , R ⁷ ,
^{R 8, R 9, R 10} , R 11, R 12, R 13,
R ¹⁴ , R ¹⁵ and R ¹⁶ are each a hydrogen atom,
Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and these may be the same or different from each other, provided that, A pair consisting of R ⁶ and R ⁷ , a pair consisting of R ⁹ and R ¹⁰ ,
The pair consisting of R ¹² and R ¹³ and the pair consisting of R ¹⁵ and R ¹⁶ are characterized in that when one of each pair is a hydrogen atom or an alkyl group, the other is an aryl group or a heterocyclic group. The electrophotographic photoreceptor according to claim 1 or 2 . 6. Y in the general formula [I] is a group represented by the general formula [III], and R ⁵ , R ⁶ , R ⁷ ,
^{R 8, R 9, R 10} , R 11, R 12, R 13,
R ¹⁴ , R ¹⁵ and R ¹⁶ are each a hydrogen atom,
Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and these may be the same or different from each other, provided that, A pair consisting of R ⁶ and R ⁷ , a pair consisting of R ⁹ and R ¹⁰ ,
When one of the pairs of R ¹² and R ¹³ and the pair of R ¹⁵ and R ¹⁶ is a hydrogen atom or an alkyl group, the other of the pair is an aryl group or a heterocyclic group. Alternatively, R ⁶ and R ⁷ , R ⁹ and R ¹⁰ , R ¹² and R ¹³ , R ¹⁵ and R ¹⁶ may be condensed to form a carbocyclic group or a heterocyclic group, and ring electrophotographic photosensitive member according to claim 1 or claim 2 may have a substituent. 7. comprising a photosensitive layer is a charge transport medium and a charge generating material, any one of claims 1 to 6, characterized in that it comprises an arylamine compound represented by the general formula [I] as a charge transporting medium The electrophotographic photoreceptor according to item 1. 8. The photosensitive layer has a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting medium, and the charge transporting layer contains an arylamine compound represented by the general formula [I]. the electrophotographic photoreceptor according to any one of claims 1 to 6, characterized in that. 9. The electrophotographic photoreceptor according to claim 8, wherein the charge generation layer contains a charge generation material and a binder. 10. A charge generating material is azo pigment, a photosensitive for electrophotography according to any one of claims 1 to 3, characterized by having a structure represented by the following general formula (VI) as the coupler body. [Chemical 7] (In the formula, B represents a nitrogen-containing heterocyclic divalent group or an aromatic hydrocarbon divalent group.)