JP2002123018A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high sensitivity to near IR rays and excellent electric characteristics, hardly causing decrease in the sensitivity after repeated use, and having stable electrification potential and excellent wear resistance. SOLUTION: The photosensitive layer 4 formed on the conductive supporting body 1 of the electrophotographic photoreceptor contains an oxotitanyl phthalocyanine of a specified crystal type as a charge generating material 2 and contains a specified bezofuran-hydroazone compound as a charge transfer material 3. Further, the photosensitive layer 4 contains a specified amount of specified polycarbonate resin as a binder resin, α-tocopherol or 2,6-di-t-butyl-4- methyl-phenol as an antioxidant, and dimethylpolysiloxane as a leveling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor using a specific crystalline oxotitanyl phthalocyanine compound as a charge generating material and a benzofuran-hydrazone compound as a charge transfer material. The present invention relates to an electrophotographic photosensitive member having high sensitivity in a region.

[0002]

2. Description of the Related Art At present, electrophotographic photoconductors (hereinafter, also simply referred to as "photoconductors") put into practical use include an inorganic photoconductor using an inorganic material and an organic photoconductor using an organic material. are categorized.

Conventionally, inorganic materials have been mainly used for electrophotographic photoreceptors from the viewpoint of both sensitivity and durability. Representative inorganic photoconductors include amorphous selenium (a-Se) and amorphous selenium arsenic (a-A).
selenium-based photoconductor composed of sSe) or the like; a photoconductor in which dye-sensitized zinc oxide (ZnO) or cadmium sulfide (CdS) is dispersed in a binder resin; a photoconductor using amorphous silicon (a-Si); There is.

The selenium-based photoconductor and the photoconductor using CdS have problems in heat resistance and storage stability.
Being toxic, its disposal causes pollution. Further, the ZnO resin dispersed photoreceptor is hardly used at present because it has low sensitivity and low durability. The a-Si photoreceptor is attracting attention as a non-polluting inorganic photoreceptor and has advantages such as high sensitivity and high durability. However, the a-Si photoreceptor uses plasma CVD (Ch
It has drawbacks such as image defects caused by a manufacturing process using an emical vapor deposition method, and a drawback that costs are increased due to low productivity. As described above, the inorganic materials have various disadvantages.

[0005] Since there are many kinds of organic materials themselves, by appropriately selecting them, it is possible to produce a non-toxic material having good storage stability. In addition, since an organic material can easily form a thin film by coating, there is an advantage that a photoreceptor can be manufactured at low cost. Further, in recent years, the sensitivity and durability of organic photoreceptors have been rapidly improved.

[0006] From the above, at present, organic materials have been used for electrophotographic photoreceptors except in special cases.

In recent years, laser beam printers which use laser light as a light source instead of the conventional white light and have advantages of high speed, high image quality and non-impact have become widespread. Development is desired. In particular, various methods using a semiconductor laser as a light source, which has remarkably progressed in recent years, have been tried among laser beams. Since the wavelength of the light source is around 800 nm, a photoconductor having a characteristic that is highly sensitive to long-wavelength light around 800 nm has been developed. It is strongly desired.

[0008] Methine squarate dyes, indoline dyes, cyanine dyes, pyrylium dyes, polyazo dyes, phthalocyanine dyes, naphthoquinone dyes, and the like have hitherto been known as organic materials meeting the demand. Methine squarate dyes, indoline dyes, cyanine dyes and pyrylium dyes can be made longer in wavelength, but lack the repetitive properties as practical stability. At present, it is difficult for polyazo dyes to have a longer wavelength, which is disadvantageous in production, and naphthoquinone dyes have difficulty in sensitivity.

A photoreceptor using a metal phthalocyanine compound among phthalocyanine dyes is disclosed in US Pat.
No. 989, JP-A-49-11136, U.S. Pat. No. 4,214,907 and British Patent No. 126.
As is apparent from the specification of No. 8422 and the like, the sensitivity peak varies depending on the central metal.
The wavelength is relatively long at 750 nm.

Japanese Unexamined Patent Publication (Kokai) No. 59-49544 discloses that an oxotitanyl phthalocyanine is vapor-deposited on a substrate to form a charge-generating layer, on which 2,6-dimethoxy-phthalocyanine is formed.
Although an electrophotographic photosensitive member provided with a charge transfer layer containing 9,10-dihydroxyanthracene as a main component is described,
The photoreceptor has a high residual potential and is somewhat restricted in usage.
The reproducibility of various electrical characteristics is disadvantageous due to the non-uniformity of the film thickness due to the vapor deposition method, and there is no choice but to be restricted in mass production of the photoconductor on an industrial scale.

In recent years, among these phthalocyanines, oxotitanyl phthalocyanines exhibiting high sensitivity have been energetically studied. Even oxotitanyl phthalocyanine alone is classified into many crystal forms based on the difference in the diffraction angle of the X-ray diffraction spectrum, as described in the Journal of the Institute of Electrophotography, Vol. 32, No. 3, page 282. Specifically, the characteristic crystal forms are shown as follows: α-type in JP-A-61-217050 and JP-A-61-239248, A-type in JP-A-62-67094, 1963-366
And JP-A-63-198067,
Mold, JP-A-63-20365, JP-A-2-825
No. 6 and JP-A-1-17066, Y-type,
JP-A-3-54265 discloses an M-type,
No. 264 describes an M-α type crystal, and Japanese Unexamined Patent Publication No. 3-128973 describes an I type crystal. JP-A-62-67
No. 094 describes type I and II crystals.

The crystal of oxotitanyl phthalocyanine whose lattice constant is known from structural analysis is C
Type, Phase I type and Phase II type. P
Phase II belongs to the triclinic system, and Phase I and C belong to the monoclinic system. From these known crystal lattice constants, when analyzing the crystal forms described in the above publication, A-type and I-type belong to Phase I-type, and α-type and B-type belong to P-type.
It belongs to the case II type, and the M type belongs to the C type. A similar analysis is described in the literature (J. of Imaging Science and Technology Vo
l.36, No. 6, 1993, p605-609).

As a problem of the photoreceptor itself, the occurrence of interference fringes, which is considered to be mainly caused by the reflection of the laser beam used for exposure on the substrate, occurs, and several techniques are known as methods for solving the problem. One known method is to increase the thickness of the charge generation layer and absorb the exposed laser beam to eliminate reflection from the substrate. However, there is a limit to the thickness that can be formed by a conventional vapor deposition method. And its control is also difficult. On the other hand, the method of forming a charge generation layer by applying a binder resin dispersion liquid has an arbitrary thickness, has good reproducibility, is easy to control, does not require a high vacuum device at the time of vapor deposition, and requires heating. Thermal decomposition and denaturation can be avoided. In addition, the binder resin dispersion liquid coating method is advantageous because there is no need to crystallize a vapor-deposited product by various methods after vapor deposition, as in the vapor deposition method, which is troublesome in industrial production.

JP-A-61-109056 discloses an electrophotographic photosensitive member in which a charge transfer layer containing a hydrazone compound and a binder resin is laminated on a charge generation layer containing an oxotitanyl phthalocyanine compound and a binder resin. To provide a photoreceptor having a sensitivity around 800 nm. The photoreceptor does not reach the sensitivity required for high image quality and high speed at present.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electronic device which is highly sensitive to near-infrared light and has excellent electrical characteristics, is unlikely to cause a decrease in sensitivity due to repeated use, has a stable charging potential and is excellent in wear resistance. An object of the present invention is to provide a photoreceptor.

[0016]

According to the present invention, a photosensitive layer formed on a conductive support is used as a charge generating substance in a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum.
7.3 °, 9.4 °, 9.6 °, 11.6 °, 13.3
°, 17.9 °, 24.1 ° and 27.2 ° show major diffraction peaks, of which the overlapping peak bundle of 9.4 ° and 9.6 ° shows the largest diffraction peak, and 27. 2
An electrophotographic photosensitive material comprising a crystalline oxotitanyl phthalocyanine having a second peak at an angle of ° and a benzofuran-hydrazone compound represented by the following general formula (I) as a charge transfer material. Body.

[0017]

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(Wherein, Ar ₁ represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Ar ₂ , Ar ₃ and Ar ₄ each represent a substituent. It represents an aryl group which may be contained, a heterocyclic group which may contain a substituent or an aralkyl group which may contain a substituent.
Is an alkyl group having 1 to 3 carbon atoms which may contain a substituent,
C1-C5 fluoroalkyl group which may contain a substituent, C1-C5 perfluoroalkyl group which may contain a substituent, C1-C3 alkoxy group, C1-C1
3 represents a dialkylamino group, a halogen atom or a hydrogen atom, and n represents an integer of 1 to 4. However, when n is 2 or more, each of a plurality of a may be the same or different, and may form a ring with each other. )

According to the present invention, oxotitanyl phthalocyanine of a specific crystal type having a strong sensitivity around 800 nm, a stable crystal type, and excellent crystal stability against solvents and heat, and benzofuran having excellent electrophotographic properties -By using in combination with a hydrazone compound, the chargeability is good, the residual potential is extremely low, and while having good durability,
An electrophotographic photoreceptor having a strong sensitivity around 800 nm can be provided.

Further, the invention is characterized in that the photosensitive layer has a laminated structure including a charge generation layer containing the charge generation material and a charge transfer layer containing the charge transfer material.

According to the present invention, the oxotitanyl phthalocyanine is contained in the charge generation layer, and the benzofuran-
By including a hydrazone compound in the charge transfer layer, it is possible to provide a laminated electrophotographic photoreceptor having good chargeability, extremely low residual potential, good durability, and high sensitivity around 800 nm. .

Further, the present invention is characterized in that the photosensitive layer comprises a single layer containing the charge generation material and the charge transfer material.

According to the present invention, by dispersing the oxotitanyl phthalocyanine and the benzofuran-hydrazone compound in a binder resin, the residual potential with good chargeability is extremely low, the durability is good, and the dispersion is 800 nm. It is possible to provide a single-layer type electrophotographic photoreceptor having strong front and rear sensitivity.

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

According to the present invention, by providing the intermediate layer, the adhesiveness between the conductive support and the photosensitive layer can be enhanced, so that an electrophotographic photosensitive member having stable sensitivity can be provided.

In the present invention, the photosensitive layer may be a polymer of a vinyl compound and a copolymer thereof as a binder resin.
It is characterized by containing at least one selected from the group consisting of a polyester resin, a polycarbonate resin, a polyarylate resin, a polysulfone resin, a polyvinyl butyral resin, a phenoxy resin, a cellulosic resin, a urethane resin, and an epoxy resin.

According to the present invention, an electrophotographic photosensitive member having excellent abrasion resistance can be provided by using a specific resin as a binder resin for the photosensitive layer.

Further, the present invention is characterized in that the binder resin contains a polycarbonate resin represented by the following general formula (II).

[0029]

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(Wherein b and c are an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, Represents an aralkyl group having 7 to 17 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and X ² represents a single bond or a substituted An alkylene group having 1 to 10 carbon atoms which may have a group, a cyclic alkylidene group having 1 to 10 carbon atoms which may have a substituent, and an arylene group having 6 to 12 carbon atoms which may have a substituent , A sulfonyl group or a carbonyl group, m and l are
U represents an integer of 1 to 4, and u represents an integer of 10 to 200. Z
Represents an alkylene group having 1 to 5 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an arylene alkyl group having 7 to 17 carbon atoms which may have a substituent. W represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms, or a substituent. Represents an alkyl ester group having 1 to 5 carbon atoms, an aryl ester group having 6 to 12 carbon atoms which may have a substituent, a carboxyl group, an aldehyde group, a hydroxyl group, a halogen atom, or a hydrogen atom. )

According to the present invention, by using a specific polycarbonate resin as a binder resin for the photosensitive layer, an electrophotographic photosensitive member having excellent abrasion resistance can be provided.

Further, the present invention is characterized in that the binder resin contains a polyester resin represented by the following general formula (III) in an amount of 5% by weight to 50% by weight based on the total amount of the binder resin.

[0033]

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(In the formula, g, h, and i represent integers of 1 to 10, and v, w, x, and y represent integers of 10 to 1,000.)

According to the present invention, by using a certain amount of a specific polyester resin together with a specific polycarbonate resin as a binder resin for the photosensitive layer, the mixing effect tends to be weak at less than 5% by weight, An electrophotographic photoreceptor excellent in abrasion resistance can be provided without causing a problem such as a decrease in viscosity as a coating liquid when the content exceeds 50% by weight.

The present invention is further characterized in that the weight ratio of the polycarbonate resin / the polyester resin is in the range of 9/1 to 7/3.

According to the present invention, by containing a polycarbonate resin and a polyester resin at a constant weight ratio, an electrophotographic photosensitive member having more excellent abrasion resistance can be provided.

Further, the present invention is characterized in that the photosensitive layer contains α-tocopherol as an antioxidant and the weight ratio of the antioxidant / charge transfer material is 0.1 / 100 or more and 5/100 or less. I do.

According to the present invention, by adding a certain amount of α-tocopherol as an antioxidant to the charge transfer material, the stability of the coating solution for the charge transfer layer can be improved and the potential characteristics can be improved. An electrophotographic photoreceptor excellent in the above can be provided.

Further, according to the present invention, the photosensitive layer contains 2,6-di-t-butyl-4-methyl-phenol as an antioxidant, and the weight ratio of the antioxidant / charge transfer material is 0.1%.
It is not less than 1/100 and not more than 50/100.

According to the present invention, the coating liquid for the charge transfer layer is prepared by containing a certain amount of 2,6-di-t-butyl-4-methyl-phenol as an antioxidant with respect to the charge transfer material. Can increase the stability of
An electrophotographic photosensitive member having excellent potential characteristics can be provided.

Further, the present invention is characterized in that the surface layer contains dimethylpolysiloxane in a weight ratio of dimethylpolysiloxane / binder resin of 0.001 / 100 or more and 5/100 or less.

According to the present invention, by including dimethylpolysiloxane as a leveling agent at a constant weight ratio to the binder resin, a photosensitive member having excellent surface properties can be obtained, and the potential characteristics can be improved. be able to.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION An electrophotographic photoreceptor according to an embodiment of the present invention comprises, on a conductive support, a specific oxotitanyl phthalocyanine compound as a charge generating substance and a specific benzofuran-hydrazone as a charge transfer substance. It is characterized by having a photosensitive layer containing a compound and a specific binder resin.

The specific oxotitanyl phthalocyanine compound used as the charge generating substance has a Bragg angle (2θ ± 0.2 °) of 7.3 ° and 9.9 in the X-ray diffraction spectrum.
4 °, 9.6 °, 11.6 °, 13.3 °, 17.9
°, 24.1 ° and 27.2 ° show major diffraction peaks, of which the overlapping peak bundle of 9.4 ° and 9.6 ° shows the maximum diffraction peak, and the peak at 27.2 ° shows It is a crystalline oxotitanyl phthalocyanine that exhibits the second maximum peak.

The method for synthesizing oxotitanyl phthalocyanine is described in Moser and Thomas, "Phthalocianine Compound" (MOSER and THOMAS. "Phthalocianine Compound").
s ''), for example, by a method in which o-phthalonitrile and titanium tetrachloride are heated and melted or heated in the presence of an organic solvent such as α-chloronaphthalene. And dichlorotitanium phthalocyanine can be obtained in good yield.
By hydrolyzing the obtained dichlorotitanium phthalocyanine with a base or water, oxotitanyl phthalocyanine is obtained. Also, oxotitanyl phthalocyanine can be obtained by heating 1,3-diiminoisoindoline and tetrabutoxytitanium in an organic solvent such as N-methylpyrrolidone. The obtained oxotitanyl phthalocyanine may contain a phthalocyanine derivative in which a hydrogen atom of a benzene ring is substituted with a substituent such as chlorine, fluorine, nitro, cyano or sulfone.

By treating such an oxotitanyl phthalocyanine composition with a water-immiscible organic solvent such as dichloroethane in the presence of water, a specific crystal form in the present invention is obtained. As a method of treating oxotitanyl phthalocyanine with a water-immiscible organic solvent in the presence of water, a method of swelling oxotitanyl phthalocyanine with water and treating it with an organic solvent, and without performing swelling treatment, Examples thereof include, but are not limited to, a method in which the compound is added to a solvent and oxotitanyl phthalocyanine powder is charged therein.

As a method of swelling oxotitanyl phthalocyanine with water, for example, a method of dissolving oxotitanyl phthalocyanine in sulfuric acid and precipitating in water to form a wet paste can be mentioned. In addition, a method of swelling oxotitanyl phthalocyanine with water using a stirring / dispersion device such as a homomixer, a paint mixer, a ball mill, and a sand mill to form a wet paste is also included, but the method is not limited to these methods. Further, the oxotitanyl phthalocyanine composition obtained by hydrolysis is subjected to a stirring treatment or a milling treatment with a mechanical strain for a sufficient time in a solution or a solution in which a binder resin is dissolved, whereby the oxo titanyl phthalocyanine composition is specified in the present invention. Is obtained.

As an apparatus used for this treatment, a homomixer, a paint mixer, a disperser, an agitator, a ball mill, a sand mill, a paint shaker, a dyno mill, an attritor, an ultrasonic disperser, and the like can be used in addition to a general stirring apparatus. it can. After the treatment, the mixture may be filtered, washed with methanol, ethanol, water, or the like, and isolated. Alternatively, after the treatment, a binder resin may be added and used as it is as a coating solution. Further, a resin to which a binder resin has been added in advance during the treatment can be used as it is as a coating solution.

Among the known crystal forms of oxotitanyl phthalocyanine, there are Y-form and M-α-form which have relatively good photosensitivity characteristics. There are other types I and M, which are crystals obtained by treating the M-α type as described in the Journal of the Institute of Electrophotography, Vol. 32, No. 3, page 282. And properties are similar, so they are included in M-α type. The above-mentioned new crystal form in the embodiment of the present invention is:
Not only does it match neither the Y-type nor the M-α-type, but it shows better properties.

Regarding the crystal type in the present embodiment, the M-α type has a Bragg angle (2θ ± 0.2) for the main peak position.
°) 7.2 °, 14.2 °, 24.0 ° and 27.1.
7.3 °, 9.4 °, 9.6 °,
It is 11.6 °, 13.3 °, 17.9 °, 24.1 ° and 27.2 °, which is clearly a crystal system completely different from the M-α form. As for the Y type, the main peak positions are 9.6 °, 11.7 °, 15.0 °, 24.1 ° and 27.1 °, which are similar to the peak positions of the crystal type in the present invention. , The two spectra differ greatly in the relationship of their relative intensities. That is, the maximum peak position is the Bragg angle (2θ ± 0.2 °), and the crystal form in the present embodiment is a peak bundle where 9.4 ° and 9.6 ° overlap, whereas the Y form is Is 27.3 °. By the way, M-α type is 27.3 °. Since the relative intensity is determined by the crystal type, the remarkable difference between the peak intensities of the two spectra is due to the fact that both crystal systems are different.

For the Y-type spectrum, see JP-A-7-2
As disclosed in JP-A-71073, a Bragg angle of 1
Two distinct peaks are observed around 8 ° and around 24 °, respectively, whereas the crystal forms in the present embodiment have Bragg angles (2θ ± 0.2 °) of 17.9 ° and 24.
At 1 °, there is a great difference in that only one peak is seen. Furthermore, the crystal-type oxotitanyl phthalocyanine of the present embodiment is superior to the photosensitivity characteristic, the repetitive use characteristic and the solvent stability.

Japanese Unexamined Patent Publication No. Hei 8-209023 discloses oxotitanyl phthalocyanine having a maximum peak at a Bragg angle (2θ ± 0.2 °) of 9.6 °. This is a new crystal type that has not been reported in the Journal of the Electrographic Society of Japan, Vol. 32, No. 3, page 282. The crystal form could not be produced by any synthesis method by the inventors of the present invention, and the crystal form in the embodiment of the present invention could not be compared with characteristics such as photosensitivity characteristics. . However, in the above crystal type, the main peak is a Bragg angle (2θ ± 0.2 °) 7.2.
2 °, 9.60 °, 11.60 °, 13.40 °, 1
4.88 °, 18.34 °, 23.62 °, 24.14
° and 27.32 °,
In the crystal form according to the present embodiment, 18.34 ° ± 0.3.
There are no peaks at 2 ° and 23.62 ° ± 0.2 °. Therefore, the new crystal form in the embodiment of the present invention is different from the above crystal form.

The specific phthalocyanine composition in the embodiment of the present invention is not limited to the one produced by the above-mentioned production method, but shows a specific peak regardless of the production method. As long as it is included. The oxotitanyl phthalocyanine thus obtained exhibits excellent properties as a charge generating substance of an electrophotographic photoreceptor. In the embodiment of the present invention,
A charge generating substance other than the oxotitanyl phthalocyanine may be used in combination. As the charge generating material used in combination, α-type, β-type, Y-type and amorphous oxotitanyl phthalocyanine which are different in crystal form from the specific oxotitanyl phthalocyanine in the present invention, other phthalocyanines, and azo pigments, anthraquinone pigments, perylene pigments And polycyclic quinone pigments and squarium pigments.

The specific benzofuran-hydrazone compound used as the charge transfer material is preferably a benzofuran-hydrazone compound represented by the following general formula (I).

[0056]

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In the general formula (I), Ar ₁ represents an arylene group optionally having a substituent and a divalent heterocyclic group optionally having a substituent.

Specific examples of Ar ₁ include a phenylene group,
Examples include a naphthylene group and a pyridylene group.

In the general formula (I), Ar2, Ar3 and A
r4 represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, an alkyl group having 1 to 5 carbon atoms which may have a substituent or a substituent. A fluoroalkyl group having 1 to 5 carbon atoms which may be contained, or 1 to 5 carbon atoms which may contain a substituent
Represents a perfluoroalkyl group.

Specific examples of Ar2, Ar3 and Ar4 include aryl groups such as phenyl, tolyl, methoxyphenyl, naphthyl, pyrenyl and biphenyl, and heterocyclic rings such as benzofuryl, benzothiazolyl, benzoxazolyl and N-ethylcarbazolyl. Groups, aralkyl groups such as methylbenzyl, methoxybenzyl and 2-thienylmethyl, alkyl groups such as methyl, ethyl and n-propyl, perfluoroalkyl groups such as trifluoromethyl, 1,1,1-trifluoroethyl and the like And fluoroalkyl groups.

In the general formula (I), a is an alkyl group having 1 to 3 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. 1 to 5 perfluoroalkyl groups, 1 to 1 carbon atoms
3 represents an alkoxy group, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and n represents an integer of 1 to 4. However, when n is 2 or more, each of a plurality of a may be the same or different,
They may form a ring with each other.

Specific examples of a include methyl, ethyl, n
-Alkyl groups such as propyl and isopropyl, alkoxy groups such as methoxy, ethoxy, n-propoxy and isopropoxy, dialkylamino groups such as dimethylamino, diethylamino and diisopropylamino, and halogen atoms such as fluorine, chlorine and bromine. Can be Generally, an electron donating substituent is preferred.

In particular, among the benzofuran-hydrazone compounds represented by the general formula (I), those which are excellent from the viewpoints of electrophotographic properties, cost, production, and the like are those in which Ar ₁ is a phenylene group or a naphthylene group, and Ar ₂ is phenyl. Groups, a p-methylphenyl group or a naphthyl group, and those wherein a is a hydrogen atom.

Next, specific examples of the benzofuran-hydrazone compound represented by the general formula (I) are shown in the following Tables 1 to 3, but the benzofuran-hydrazone compound of the present invention is not limited thereto.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

By containing the benzofuran-hydrazone compound represented by the general formula (I) as a charge transfer material, an electrophotographic photosensitive member having excellent charging characteristics can be provided.

Examples of the specific binder resin include vinyl polymers such as polymethyl methacrylate, polystyrene and polyvinyl chloride, copolymers thereof, polycarbonate resin, polyester resin, polyester carbonate resin, polysulfone resin, phenoxy resin and epoxy resin. And silicone resin. These may be used alone or as a mixture of two or more kinds, and a partially crosslinked thermosetting resin may also be used. In particular, a polycarbonate resin represented by the following general formula (II) and a mixed resin of a polycarbonate resin represented by the following general formula (II) and a polyester resin represented by the following general formula (III) are suitable as the binder resin. This further enhances the abrasion resistance of the photoconductor.

[0070]

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In the general formula (II), b and c are each
An alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent An alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms,
Represents a halogen atom or a hydrogen atom. X ² may be a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, a cyclic alkylidene group having 1 to 10 carbon atoms which may have a substituent, or a substituent. Represents an arylene group, a sulfonyl group, or a carbonyl group having 6 to 12 carbon atoms;
And 1 are integers of 1 to 4, and u is an integer of 10 to 200.

In the general formula (II), Z represents an optionally substituted alkylene group having 1 to 5 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an arylene alkyl group having 7 to 17 carbon atoms. Represent. W represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms, or a substituent. Represents an alkyl ester group having 1 to 5 carbon atoms, an aryl ester group having 6 to 12 carbon atoms which may have a substituent, a carboxyl group, an aldehyde group, a hydroxyl group, a halogen atom, or a hydrogen atom.

Next, specific examples of the polycarbonate resin represented by the general formula (II) include those having the structures shown in Table 4 below, but are not limited thereto.

[0074]

[Table 4]

[0075]

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In the general formula (III), g, h and i are
Represents an integer of 1 to 10, and v, w, x and y are 10 to
Represents an integer of 1000.

The polyester resin of the general formula (III) is
5% by weight or more based on the entire binder resin
0% by weight or less, more preferably 10% by weight or more and 30% by weight or less. If the amount is less than 5% by weight, the effect of mixing tends to be weak. If the amount exceeds 50% by weight, problems such as a decrease in viscosity of the coating liquid may be caused.

The benzofuran-hydrazone compound represented by the general formula (I) is added to 1 part by weight of the binder resin.
It is preferably used in an amount of 0.2 to 1.5 parts by weight, more preferably 0.3 to 1.2 parts by weight.

FIG. 1 is a cross-sectional view schematically showing one example of an electrophotographic photosensitive member having a laminated photosensitive layer. FIG. 2 is a cross-sectional view schematically illustrating an example of an electrophotographic photosensitive member having a dispersion type photosensitive layer. FIG. 3 is a cross-sectional view showing an example having an intermediate layer 7 in the electrophotographic photoreceptor of FIG. FIG.
FIG. 3 is a cross-sectional view illustrating an example having an intermediate layer 7 in the electrophotographic photosensitive member of FIG. The electrophotographic photosensitive member of FIG.
This is a function-separated type photoreceptor having a stacked type photosensitive layer 4 on which a charge generation layer 5 containing a charge generation substance 2 and a charge transfer layer 6 containing a charge transfer substance 3 are formed. The electrophotographic photoreceptor shown in FIG. 2 is obtained by dispersing a charge generating substance 2 on a conductive support
And a charge-transfer substance 3 and a dispersion-type photosensitive layer 14. 3 and 4, the intermediate layer 7 is provided between the conductive support 1 and the photosensitive layer 4 or 14 as a commonly used known intermediate layer. By providing the intermediate layer 7, the adhesiveness between the conductive support and the photosensitive layer can be increased, so that an electrophotographic photosensitive member with stable sensitivity can be provided.

The configuration of the electrophotographic photosensitive member according to the embodiment of the present invention includes a laminated type as shown in FIG. 1, a single-layer type as shown in FIG. 2, or an intermediate layer 7 as shown in FIGS. It can be a laminated type or a single layer type. Note that the binder resin is contained in the charge generation layer 5 and the charge transfer layer 6 in the laminated type, and in the photosensitive layer 14 in the dispersion type.

Hereinafter, the electrophotographic photosensitive member according to the present embodiment will be described separately for the case of a laminated photosensitive member and the case of a single-layer photosensitive member.

In the case of a stacked type photoreceptor, the above-mentioned crystalline oxotitanyl phthalocyanine is used as the charge generating substance 2 in the charge generating layer 5, and the above-mentioned other charge generating substance 2 may be contained. . The charge transfer layer 6 contains the benzofuran-hydrazone compound as the charge transfer substance 3, and may contain various additives such as a leveling agent, an antioxidant, and a sensitizer as needed. Particularly, antioxidants include α-tocopherol and 2,6-di-t
-Butyl-4-methyl-phenol is preferred. α-
0.1% by weight of tocopherol based on the charge transfer material 3
Preferably, it is contained in an amount of not less than 5% by weight and not more than 5% by weight. Thereby, the potential characteristics are excellent, and the stability as a coating solution is also enhanced.

As a method for forming each layer, a known method such as sequentially applying a coating solution obtained by dissolving or dispersing a substance contained in the layer in a solvent can be applied.

The charge generation layer 5 can be formed by vacuum deposition, sputtering, or CVD (Chemical Vapor D).
eposition) and a coating method. In the coating method, the charge generating substance 2 is dissolved in a solvent,
Or pulverized and dispersed by a ball mill, sand grinder, paint shaker, ultrasonic disperser, etc., add a binder resin and a solvent as needed, and in the case of a sheet, a baker applicator, bar coater, casting and spin coating, etc. In the case of a drum, the charge generation layer 5 is formed by a spray method, a vertical ring method, a dip coating method, or the like.

In particular, in the method of applying the dispersion liquid, the thickness of the coating layer can be made to be an arbitrary thickness, the exposed laser beam can be absorbed and the reflection from the substrate can be eliminated, and the reproducibility is good and the control is easy. In addition, the method of applying the dispersion liquid does not require a high vacuum device at the time of vapor deposition as compared with the vapor deposition method, and can avoid thermal decomposition and thermal denaturation due to heating, such as crystallization of the vapor deposited product after vapor deposition. This is advantageous because there is no trouble in industrial production.

Solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as benzene, toluene and xylene. And aprotic polar solvents such as N, N-dimethylformamide and dimethylsulfoxide can be used alone or in combination of two or more.

The thickness of the charge generation layer 5 is 0.05 to
It is preferably 5 μm, more preferably 0.08 to 1 μm.

As a method of forming the charge transfer layer 6, the charge transfer material 3 is dissolved in a solvent, a binder resin is added, and in the case of a sheet, a baker applicator, a bar coater, casting and spin coating, and in the case of a drum, The charge transfer layer 6 is formed by applying a spray method, a vertical ring method, a dip coating method, or the like.

Examples of the binder resin include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, polycarbonate resins, polyester resins, polyester carbonate resins, polysulfone resins, phenoxy resins, epoxy resins, and silicone resins. Resins. These may be used singly or as a mixture of two or more kinds. In addition, a copolymer of a monomer necessary for constituting the resin, and a thermosetting resin partially crosslinked can also be used.

Examples of the solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; N
Aprotic polar solvents such as dimethylformamide and dimethylsulfoxide can be used.

The thickness of the charge transfer layer 6 is preferably 5 to 60 μm, more preferably 10 to 40 μm.

Usually, the charge transfer layer 6 is formed on the charge generation layer 5, but the reverse is also possible. Further, as the outermost surface layer, for example, a conventionally known overcoat layer mainly composed of a thermoplastic or thermosetting polymer may be provided.

In the case of a single layer type photosensitive layer, the above-mentioned crystalline oxotitanyl phthalocyanine is dispersed in the charge transfer layer 6 having the same compounding ratio as that of the charge transfer layer 6 in the laminated type photoreceptor. The particle size of the oxotitanyl phthalocyanine is
It is necessary to be sufficiently small, and it is preferable to use it at 1 μm or less. If the amount of the charge generating substance 2 dispersed in the photosensitive layer 14 is too small, the sensitivity is insufficient, and if the amount is too large, adverse effects such as lowering of chargeability and sensitivity are caused.
% By weight, more preferably 1 to 20% by weight. The thickness of the photosensitive layer 14 is preferably 5 to 50 μm, more preferably 10 to 40 μm.

The photosensitive layer 14 in the single-layer type photoreceptor also has a conventionally known plasticizer for improving film forming properties, flexibility and mechanical strength, an additive for suppressing residual potential, dispersion stability. A dispersing aid for improving the properties, a leveling agent for improving the coating properties, a surfactant, a silicone oil, a fluorinated oil, and other additives may be added. Particularly, as the leveling agent, dimethylpolysiloxane is suitable, and it is preferable that the content is 0.001% by weight or more and 5% by weight or less based on the binder resin. As a result, a photoconductor having excellent surface properties can be obtained, and the potential characteristics can be improved.

As the conductive support 1 used in the embodiment of the present invention, one having a substrate itself having conductivity,
For example, aluminum, aluminum alloys, copper, zinc,
Stainless steel, nickel, titanium and the like can be used. In addition, plastic and paper on which aluminum, gold, silver, copper, zinc, nickel, titanium, indium oxide, tin oxide, and the like are deposited, plastic and paper containing conductive particles, and plastic containing a conductive polymer are used. be able to. As their shapes, drums, sheets, seamless belts, and the like can be used.

As the intermediate layer 7 provided between the conductive support 1 and the photosensitive layer 4 or 14, an inorganic layer such as an aluminum anodic oxide film, aluminum oxide, aluminum hydroxide and titanium oxide, as well as polyvinyl alcohol, polyvinyl Butyral, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, polyamide, casein, and N
-Methoxymethylated nylon and the like are used. Further, particles such as titanium oxide, tin oxide and aluminum oxide may be dispersed therein.

The characteristic of the electrophotographic photoreceptor according to the embodiment of the present invention obtained as described above is that the oxotitanyl phthalocyanine used for the photoreceptor has a high sensitivity even in a long wavelength range, and thus the photoreceptor in the long wavelength range can be used. In particular, it has an optimum photosensitive wavelength range for a semiconductor laser and an LED (Light Emitting Diode). The oxotitanyl phthalocyanine used for the photoreceptor is characterized by having a stable crystal form, excellent crystal stability against solvents and heat, and excellent photosensitivity and repeated use characteristics as the photoreceptor. These characteristics are not only the above-mentioned properties at the time of producing oxotitanyl phthalocyanine, but also have a great advantage in producing and using an electrophotographic photosensitive member.

[0098]

EXAMPLES Hereinafter, a method for manufacturing a photoreceptor using the above-described materials and potential characteristics will be specifically described based on examples. However, the present invention is limited to the following examples unless it exceeds the gist. Not something.

(Production Example 1) o-phthalodinitrile 40
g, titanium tetrachloride 18 g and α-chloronaphthalene 5
The mixture was heated and stirred at 200 to 250 ° C. for 3 hours in a nitrogen atmosphere, allowed to react, cooled to 100 to 130 ° C., then filtered while hot, and α-chloronaphthalene 20 heated to 100 ° C.
After washing with 0 ml, a crude product of dichlorotitanium phthalocyanine was obtained. This crude product was washed with 200 ml of α-chloronaphthalene and then with 200 ml of methanol at room temperature, and further washed with 500 ml of methanol for 1 hour under hot suspension. After filtration, the obtained crude product was dissolved in 500 ml of water.
After repeated hot suspension washing until the pH reached 6 to 7, drying was performed to obtain oxotitanyl phthalocyanine intermediate crystals.

An X-ray diffraction spectrum of the obtained oxotitanyl phthalocyanine intermediate crystal was measured under the following conditions. The oxotitanyl phthalocyanine obtained in Production Examples 1 to 3 described below was also measured under the same conditions. X-ray source CuKα = 1.54050 ° Voltage 40 kV Current 50 mA Start angle 5.0 deg. Stop angle 30.0 deg. Step angle 0.02 deg. Measurement time 0.5 deg. / Sec Measurement method θ / 2θ Scan method

FIG. 5 is a diagram showing an X-ray diffraction spectrum of the oxotitanyl phthalocyanine intermediate crystal obtained during the production of Production Example 1 of the present invention. This intermediate crystal has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 ° and diffraction peaks at 7.4 °, 9.6 ° and 27.3 °. It can be seen that it is a crystal type oxotitanyl phthalocyanine called a Y type described in 8256 and JP-A-7-271073.

1.0 g of these crystals was dissolved in methyl ethyl ketone 3
After mixing with 0 g, the mixture was milled with glass beads having a diameter of 2 mm by a paint conditioner (manufactured by Red Level Co., Ltd.), washed with methanol, and then dried to obtain oxotitanyl phthalocyanine crystals.

FIG. 6 is a view showing an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 1 of the present invention. This crystal has a Bragg angle (2θ ± 0.2 °)
The highest diffraction peak was shown in the overlapping peak bundle of 9.4 ° and 9.6 °, and 7.3 °, 9.4 °, 9.6 °, 1
It can be seen that the oxotitanyl phthalocyanine of the specific crystalline form in the present invention has diffraction peaks at 1.6 °, 13.3 °, 17.9 °, 24.1 ° and 27.2 °.

(Production Example 2) 1.0 g of the oxotitanyl phthalocyanine intermediate crystal obtained in the middle of Production Example 1 and polybutyral (Eslec BL-1 manufactured by Sekisui Chemical Co., Ltd.)
6 g was mixed with 40 g of methyl ethyl ketone, and milled with glass beads having a diameter of 2 mm using a bead mill to obtain crystals of oxotitanyl phthalocyanine.

FIG. 7 is a view showing an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 2 of the present invention. This crystal has a Bragg angle (2θ ± 0.2 °)
The highest diffraction peak was shown in the overlapping peak bundle of 9.4 ° and 9.6 °, and 7.3 °, 9.4 °, 9.6 °, 1
It has diffraction peaks at 1.6 °, 13.3 °, 17.9 °, 24.1 ° and 27.2 °, and further 14.1 ° to 1
At 4.9 °, having a plurality of diffraction peaks having the same intensity, a group of peaks having a trapezoidal shape and having difficulty in separating peaks was shown, and it was found that the oxotitanyl phthalocyanine of the specific crystal type in the present invention was used. .

(Production Example 3) 1.0 g of the oxotitanyl phthalocyanine intermediate crystal obtained in the middle of Production Example 1 and polybutyral (Eslec BL-1 manufactured by Sekisui Chemical Co., Ltd.)
4 g and 0.2 g of a vinyl chloride-vinyl acetate copolymer resin (Slec M-1 manufactured by Sekisui Chemical Co., Ltd.) were mixed with 40 g of methyl ethyl ketone, and milled together with glass beads having a diameter of 2 mm by a paint conditioner to obtain oxotitanyl phthalocyanine. Was obtained.

FIG. 8 is a view showing an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 3 of the present invention. This crystal has a Bragg angle (2θ ± 0.2 °)
The highest diffraction peak was shown in the overlapping peak bundle of 9.4 ° and 9.6 °, and 7.3 °, 9.4 °, 9.6 °, 1
It has diffraction peaks at 1.6 °, 13.3 °, 17.9 °, 24.1 ° and 27.2 °, from 14.1 ° to 14.9.
In °, a plurality of diffraction peaks having the same intensity are shown to indicate a trapezoidal shape, which is a group of difficult-to-separate peaks. A peak having about half the intensity of the peak bundle exists as a shoulder peak of the peak bundle. It turns out that it is oxo titanyl phthalocyanine of a specific crystal type in the present invention.

(Production Example 4) The benzofuran-hydrazone compound shown in No. 1 was produced.

5-Formyl-2- (4 '-(bis (p
-Tolyl) amino) phenyl) benzo [b] furan
0 g (1.0 equivalent) was dissolved in 6 ml of ethanol.
0.35 g (1.2 equivalents) of phenyl-N-methylhydrazine and 0.05 ml of acetic acid as a catalyst were added at room temperature, followed by heating and stirring at 60 to 70 ° C for 5 hours. After confirming the completion of the reaction by thin film chromatography (TLC), the reaction mixture was allowed to cool, and the resulting solid was filtered off and washed with ethanol. The solid was recrystallized from ethanol to obtain 1.15 g of yellow crystals of the target benzofuran-hydrazone compound (Exemplary Compound No. 1). The yield was 92.0%.

The structure of the thus obtained benzofuran-hydrazone compound (Exemplary Compound No. 1) is represented by ¹ H
-NMR, usually ¹³ C-NMR and DEPT135 ¹³ C
-Confirmed by measuring NMR.

FIG. 9 is a graph showing ¹ H-formation of a benzofuran-hydrazone compound (exemplary compound No. 1) in deuterated chloroform.
It is an NMR spectrum. FIG. 10 shows a benzofuran-hydrazone compound (exemplified compound N) in deuterated chloroform.
o. It is a ¹³ C-NMR spectrum of 1). FIG.
DEPT135 ¹³ C-NMR of benzofuran-hydrazone compound (exemplified compound No. 1) in deuterated chloroform
It is a spectrum. These NMR signals correspond to the target benzofuran-hydrazone compound (Exemplified Compound N).
o. The structure of 1) is well supported.

Example 1 An aluminum-evaporated polyester film was used as a conductive support. On this support, 2.1 g of titanium oxide and copolymer nylon (CM80 manufactured by Toray Industries, Inc.) were used.
00) 3.9 g was added to a mixed solvent of methyl alcohol 32.9 g and dichloroethane 61.1 g, and a solution dispersed in a paint shaker for 12 hours was applied and dried to form an intermediate layer having a thickness of 1 μm. did.

1 part by weight of the crystalline oxotitanyl phthalocyanine obtained in Production Example 1 and 1 part by weight of polybutyral (Eslec BL-1 manufactured by Sekisui Chemical Co., Ltd.) were mixed with 70 parts by weight of methyl ethyl ketone, and a paint conditioner was prepared. 2m in diameter by device (manufactured by Red Level)
It was prepared by dispersion treatment with m glass beads. The prepared solution was applied on the intermediate layer and dried to obtain a film thickness of 0.4
A μm charge generation layer was formed.

Illustrative Compound No. as a charge transfer material 10 parts by weight of benzofuran-hydrazone compound 1, 8 parts by weight of a polycarbonate resin (II-1) and 2 parts by weight of a polyester resin (III) as a binder resin, 0.2 parts by weight of α-tocopherol as an antioxidant, and a leveling agent Polydimethylsiloxane 0.000
2 parts by weight and mixed with tetrahydrofuran as a solvent.
A 5% by weight solution was prepared. The prepared solution was applied on the previously formed charge generation layer to form a charge transfer layer having a dry film thickness of 20 μm.

As described above, a laminated electrophotographic photosensitive member sample 1 composed of the charge generation layer and the charge transfer layer was obtained.

Example 2 A solution obtained by the dispersion treatment of Example 1 was applied directly on a support made of an aluminum-evaporated polyester film as a conductive support, and dried to obtain a film having a thickness of 0.4 μm. Was formed.

Illustrative Compound No. as a charge transfer material 10 parts by weight of a benzofuran-hydrazone compound represented by 3,
Polycarbonate resin (II-1) as binder resin
7 parts by weight and 3 parts by weight of the polyester resin (III),
0.5 parts by weight of 2,6-di-t-butyl-4-methyl-phenol was mixed as an antioxidant, and a 15% by weight solution was prepared using tetrahydrofuran as a solvent. The prepared solution is applied on the previously formed charge generating layer, and the dried film thickness 2
Forming a charge transfer layer of 0 μm, and separating the photoreceptor sample 2
I got

Example 3 A charge generation layer was prepared in the same manner as in Example 1 except that a vinyl chloride-vinyl acetate copolymer resin (Slec BM-1 manufactured by Sekisui Chemical Co., Ltd.) was used as the resin for the charge generation layer. Was formed.

Illustrative Compound No. as a charge transfer material 10 parts by weight of a benzofuran-hydrazone compound represented by 8,
The polycarbonate resin (II-1) 9 as a binder
Parts by weight and 1 part by weight of polyester resin (III), 0.2 parts by weight of α-tocopherol as an antioxidant, and 0.1 parts by weight of polydimethylsiloxane as a leveling agent.
0002 parts by weight were mixed to prepare a 15% by weight solution using tetrahydrofuran as a solvent. The prepared solution was applied on the previously formed charge generation layer to form a charge transfer layer having a dry film thickness of 20 μm.

(Example 4) A polyester film deposited with aluminum was used as a conductive support, and 2.1 g of titanium oxide and nylon copolymer (CM80 manufactured by Toray Industries, Inc.) were placed on the support.
00) 3.9 g was added to a mixed solvent of methyl alcohol 32.9 g and dichloroethane 61.1 g, and a solution dispersed in a paint shaker for 12 hours was applied and dried to form an intermediate layer having a thickness of 1 μm. did.

The same procedure as in Example 1 was carried out except that the crystalline oxotitanyl phthalocyanine obtained in Production Example 2 was used as the charge generating substance.
A 4 μm charge generation layer was formed.

Illustrative Compound No. as a charge transfer material 10 parts by weight of the benzofuran-hydrazone compound represented by No. 1 and a polycarbonate resin (II-
1) 8 parts by weight and 2 parts by weight of a polyester resin (III), 2,6-di-t-butyl-4-as an antioxidant
0.5 parts by weight of methyl-phenol and 0.0002 parts by weight of polydimethylsiloxane as a leveling agent were mixed to prepare a 15% by weight solution using tetrahydrofuran as a solvent. The prepared solution was applied onto the previously formed charge generation layer to form a charge transfer layer having a dry film thickness of 25 μm.

As described above, a function-separated type photoconductor sample 4 comprising a charge generation layer and a charge transfer layer was obtained.

(Example 5) As a charge transfer material, Compound No. A function-separated photoconductor sample 5 was obtained in the same manner as in Example 4, except that the benzofuran-hydrazone compound represented by No. 13 was used.

Example 6 An aluminum-evaporated polyester film was used as a conductive support. On this support, 2.1 g of titanium oxide and copolymer nylon (CM80 manufactured by Toray Industries, Inc.) were used.
00) 3.9 g was added to a mixed solvent of methyl alcohol 32.9 g and dichloroethane 61.1 g, and a solution dispersed in a paint shaker for 12 hours was applied and dried to form an intermediate layer having a thickness of 1 μm. did.

The same procedure as in Example 1 was repeated, except that the crystalline oxotitanyl phthalocyanine obtained in Production Example 3 was used as the charge generating substance.
A 4 μm charge generation layer was formed.

Illustrative Compound No. as a charge transfer material. 10 parts by weight of the benzofuran-hydrazone compound represented by 1,
Polycarbonate resin (II-1) as binder resin
8 parts by weight and 2 parts by weight of the polyester resin (III),
A mixture of 0.5 parts by weight of 2,6-di-t-butyl-4-methyl-phenol as an antioxidant and 0.0002 parts by weight of polydimethylsiloxane as a leveling agent, and a solution of 15% by weight using tetrahydrofuran as a solvent. Was prepared. The prepared solution was applied onto the previously formed charge generation layer to form a charge transfer layer having a dry film thickness of 25 μm.

Thus, a function-separated type photoreceptor sample 6 comprising a charge generation layer and a charge transfer layer was obtained.

(Example 7) As a charge transfer material, exemplified compound No. A function-separated photoconductor sample 7 was obtained in the same manner as in Example 6, except that the benzofuran-hydrazone compound represented by 24 was used.

Example 8 An aluminum-evaporated polyester film was used as a conductive support. On this support, 2.1 g of titanium oxide and copolymer nylon (CM80 manufactured by Toray Industries, Inc.) were used.
00) 3.9 g was added to a mixed solvent of methyl alcohol 32.9 g and dichloroethane 61.1 g, and a solution dispersed in a paint shaker for 12 hours was applied and dried to form an intermediate layer having a thickness of 1 μm. did.

1 part by weight of the crystalline form of oxotitanyl phthalocyanine obtained in Production Example 1 was used. 1
10 parts by weight of a benzofuran-hydrazone compound represented by No. 9 and a polycarbonate resin (II-
1) 8 parts by weight, 2 parts by weight of polyester resin (III), and 0.5 part by weight of 2,6-di-t-butyl-4-methyl-phenol as an antioxidant, and 15 parts by weight using tetrahydrofuran as a solvent % Solution was prepared. The prepared solution was dispersed together with glass beads having a diameter of 2 mm using a paint conditioner (manufactured by Red Level). The solution obtained by this dispersion was applied onto the intermediate layer to form a photosensitive layer having a dry film thickness of 25 μm.

As described above, a single-layer type photoreceptor sample 8 in which the charge generation material was dispersed in the charge transfer layer was obtained.

Example 9 A laminated photoreceptor sample 9 was obtained in the same manner as in Example 1 except that α-tocopherol was not added to the charge transfer layer.

(Example 10) 2,6-Di-
A laminated photoreceptor sample 10 was prepared in the same manner as in Example 2 except that t-butyl-4-methyl-phenol was not added.
I got

Example 11 A laminated photoreceptor sample 11 was prepared in the same manner as in Example 1 except that polydimethylsiloxane was not added to the charge transfer layer. No coating film was obtained.

Example 12 A laminated photoreceptor sample 12 was obtained in the same manner as in Example 1, except that a polycarbonate resin containing bisphenol A as a monomer component was used as the binder resin for the charge transfer layer.

Example 13 The same procedure as in Example 1 was repeated except that 4 parts by weight of the polycarbonate resin (II-1) and 6 parts by weight of the polyester resin (III) were used as the binder resin for the charge transfer layer. Photoconductor sample 13 was obtained.

(Example 14) 2,6 as an antioxidant
A single-layer photoreceptor sample 14 was obtained in the same manner as in Example 8, except that -di-t-butyl-4-methyl-phenol was not added.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the intermediate crystal of oxotitanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. Function-separated photoreceptor sample 1
5 was obtained.

Comparative Example 2 The same procedure as in Example 2 was carried out except that the intermediate crystal of oxotitanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. 5 obtained in the middle of Production Example 1 was used as the charge generating substance. Function-separated photoreceptor sample 1
6 was obtained.

(Comparative Example 3) Lamination was performed in the same manner as in Example 1 except that a 4- (diethylamino) -benzaldehyde-N, N-diphenylhydrazone compound, which was a conventionally known charge transfer material, was used as the charge transfer material. A photoreceptor sample 17 was obtained.

(Comparative Example 4) As a charge transfer material, N, N'-bis- (3-methylphenyl) -N, N'-bis- (phenyl) -benzidine (TPD) which is a conventionally known charge transfer material is used. A laminated photoreceptor sample 18 was obtained in the same manner as in Example 1 except for using.

Comparative Example 5 The procedure of Example 8 was repeated, except that the intermediate crystal of oxotitanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. A single-layer electrophotographic photosensitive member sample 19 was obtained.

Comparative Example 6 The procedure of Example 8 was repeated except that a 4- (diethylamino) -benzaldehyde-N, N-diphenylhydrazone compound, which was a conventionally known charge transfer substance, was used as the charge transfer substance. A layer type photoreceptor sample 20 was obtained.

Comparative Example 7 Production Example 1 as a charge generating substance
The intermediate crystal of oxotitanyl phthalocyanine having the X-ray diffraction pattern of FIG.
A laminated photoreceptor sample 21 was obtained in the same manner as in Example 2 except that a (diethylamino) -benzaldehyde-N, N-diphenylhydrazone compound was used and α-tocopherol was not added to the charge generation layer.

Comparative Example 8 Production Example 1 as a charge generating substance
The intermediate crystal of oxotitanyl phthalocyanine having the X-ray diffraction pattern of FIG.
A laminated photoreceptor sample 22 was obtained in the same manner as in Example 11, except that the (diethylamino) -benzaldehyde-N, N-diphenylhydrazone compound was used. Could not be obtained.

(Comparative Example 9) Production Example 1 as a charge generating substance
The intermediate crystal of oxotitanyl phthalocyanine having the X-ray diffraction pattern of FIG.
Using a (diethylamino) -benzaldehyde-N, N-diphenylhydrazone compound, 6 parts by weight of a polycarbonate (II-1) and 4 parts by weight of a polyester resin (III) were added as a binder resin, and no antioxidant and leveling agent were added. Except for this, a laminated photoreceptor sample 23 was obtained in the same manner as in Example 1.

Examples 1 to 14 and Comparative Examples 1 to 9
Table 5 shows the configurations of Samples 1 to 23 prepared in the above.

[0149]

[Table 5]

(Evaluation) The electrophotographic photoreceptor produced as described above was tested using an electrostatic recording paper tester (Kawaguchi Electric Co .; EP
A-8200) to evaluate the electrophotographic characteristics. Regarding the laminated electrophotographic photoreceptor, applied voltage: -6 kV and static: No. 780 nm monochromatic light (irradiation light: 2 μW / c) spectrally separated by an interference filter under the measurement conditions of 3.
m ² ), the exposure E _1/2 (μJ / cm ² ) and the initial potential V ₀ (−volt) required to attenuate the voltage from −500 V to −250 V were measured. For the single-layer type electrophotographic photoreceptor, the applied voltage: +6 kV and the static: N
o. 780n, which was separated by an interference filter under the measurement conditions of 3
+50 by m monochromatic light (irradiation light: 10 μW / cm ² )
Exposure amount E required to attenuate from 0 V to +250 V
_1/2 (μJ / cm ² ) and initial potential V ₀ (+ volt) were measured.

Further, a commercially available digital copying machine (AR5130 manufactured by Sharp Corporation) was modified to use the photosensitive member shown in Table 5 for the drum portion, and to perform continuous exposure without consuming toner (Non Copy Aging). Was carried out 30,000 times, and before and after that, the charged potential and E _1/2 were measured using the electrostatic recording paper test apparatus. In a high temperature and high humidity environment (35 ° C, 8
(5%) was continuously performed 30,000 times (Non Copy Aging), and before and after that, the residual potential was measured. Further, the degree of reduction of the photoreceptor film thickness was evaluated using a wear tester (manufactured by Suga Test Instruments Co., Ltd.). The measurement conditions were as follows: abrasive: aluminum oxide # 2000, load: 200 g · f, and number of times of friction: 10,000 times.

Table 6 shows the evaluation results. Table 7 shows the results of visually observing the uniformity of the film on the surface of the photoreceptor.
Shown in

[0153]

[Table 6]

[0154]

[Table 7]

As shown in Table 6, in each of Examples 1 to 8, the potential deterioration of each of the samples after the durability test (30,000 times) of the charging potential was smaller than that of Comparative Examples 1 to 4, which were the conventional samples. It can be seen that the characteristics are sufficiently small, the initial sensitivity (half-exposure amount) is sufficiently high as compared with the comparative example, and the sensitivity deterioration is small even after the durability test. Also, it can be seen that the residual potential rise after the durability test (30,000 times) under high temperature and high humidity in Examples 1 to 8 is sufficiently small as compared with the conventional sample.

Further, as shown in Table 7, Example 11 in which polydimethylsiloxane was not added as a leveling agent,
In Comparative Examples 8 and 9, it can be seen that a citron skin-like defect occurs on the entire surface.

[0157]

As described above, according to the present invention, by using a specific crystalline oxotitanyl phthalocyanine as a charge generating substance and using a benzofuran-hydrazone compound as a charge transfer substance, the sensitivity in a long wavelength region is significantly improved. An electrophotographic photosensitive member that is high and has high durability can be provided. Therefore, the electrophotographic photoreceptor according to the present invention is suitable as a photoreceptor such as a laser printer and a digital copier using a semiconductor laser beam as a light source, which has been significantly developed recently.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically illustrating an example of an electrophotographic photosensitive member having a stacked photosensitive layer.

FIG. 2 is a cross-sectional view schematically illustrating an example of an electrophotographic photosensitive member having a dispersion type photosensitive layer.

FIG. 3 is a cross-sectional view showing an example having an intermediate layer 7 in the electrophotographic photoreceptor of FIG.

FIG. 4 is a cross-sectional view showing an example having an intermediate layer 7 in the electrophotographic photoreceptor of FIG.

FIG. 5 is a view showing an X-ray diffraction spectrum of an oxotitanyl phthalocyanine intermediate crystal obtained during the production of Production Example 1 of the present invention.

FIG. 6 is a view showing an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 1 of the present invention.

FIG. 7 is a view showing an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 2 of the present invention.

FIG. 8 is a view showing an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 3 of the present invention.

FIG. 9 is a ¹ H-NMR spectrum of a benzofuran-hydrazone compound (Exemplary Compound No. 1) in deuterated chloroform.

FIG. 10 is a ¹³ C-NMR spectrum of a benzofuran-hydrazone compound (Exemplary Compound No. 1) in deuterated chloroform.

FIG. 11 shows DEPT135 ¹³ of a benzofuran-hydrazone compound (exemplary compound No. 1) in deuterated chloroform.
It is a C-NMR spectrum.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Charge generation material 3 Charge transfer material 4, 14 Photosensitive layer 5 Charge generation layer 6 Charge transfer layer 7 Intermediate layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/3417 C08K 5/3417 C08L 69/00 C08L 69/00 83/04 83/04 101/00 101 / 00 G03G 5/05 101 G03G 5/05 101 104 104B 5/14 101 5/14 101 // (C08L 69/00 (C08L 69/00 67:02) 67:02) F term (reference) 2H068 AA13 AA14 AA16 AA19 AA20 AA34 AA35 AA41 BA12 BA24 BA39 BB02 BB16 BB20 BB23 BB25 BB26 BB27 BB29 BB30 BB34 BB35 BB40 BB69 FA03 4J002 AA001 AB011 BE051 CF101 CF102 CF161 CG011 CG021 CH081 CK020 CN03 CN030

Claims (11)

[Claims] 1. A photosensitive layer formed on a conductive support,
As a charge generating substance, in the X-ray diffraction spectrum, 7.3 °, 9.4 °, and 9.30 ° Bragg angles (2θ ± 0.2 °).
6 °, 11.6 °, 13.3 °, 17.9 °, 24.1
And the main diffraction peaks at 27.2 °, the overlapping peak bundle of 9.4 ° and 9.6 ° indicates the maximum diffraction peak, and the peak at 27.2 ° is the second largest peak. An electrophotographic photoreceptor comprising a crystalline oxotitanyl phthalocyanine represented by the formula: and a benzofuran-hydrazone compound represented by the following general formula (I) as a charge transfer material. Embedded image (In the formula, Ar ₁ represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Ar
₂ , Ar ₃ and Ar ₄ each represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent or an aralkyl group which may have a substituent. a is an alkyl group having 1 to 3 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent, a perfluoroalkyl group having 1 to 5 carbon atoms which may have a substituent ,
An alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom,
Represents an integer of 1 to 4. However, when n is 2 or more,
Each of a plurality of a may be the same or different, and may form a ring with each other. ) 2. The electron according to claim 1, wherein the photosensitive layer has a laminated structure including a charge generation layer containing the charge generation material and a charge transfer layer containing the charge transfer material. Photoreceptor. 3. The electrophotographic photoreceptor according to claim 1, wherein said photosensitive layer comprises a single layer containing said charge generating substance and said charge transfer substance. 4. The electrophotographic photosensitive member according to claim 1, wherein an intermediate layer is provided between the conductive support and the photosensitive layer. 5. The photosensitive layer, wherein the binder resin is a polymer of a vinyl compound and a copolymer thereof, a polyester resin, a polycarbonate resin, a polyarylate resin, a polysulfone resin, a polyvinyl butyral resin, a phenoxy resin, a cellulosic resin, and a urethane resin. 2. The electrophotographic photoreceptor according to claim 1, comprising at least one selected from the group consisting of a resin and an epoxy resin. 6. The binder resin according to the following general formula (I)
The electrophotographic photoreceptor according to claim 5, further comprising a polycarbonate resin represented by I). Embedded image (In the formula, b and c each have an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, Carbon number 7
To 17 aralkyl groups, alkenyl groups having 2 to 5 carbon atoms,
Represents an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and X ² may be a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, or may have a substituent. A cyclic alkylidene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms which may have a substituent, a sulfonyl group, or a carbonyl group, m and l are integers of 1 to 4, u is Indicates an integer of 10 to 200. Z is an alkylene group having 1 to 5 carbon atoms which may have a substituent;
12 represents an arylene group and an arylene alkyl group having 7 to 17 carbon atoms. W represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms, or a substituent. An alkyl ester group having 1 to 5 carbon atoms, an aryl ester group having 6 to 12 carbon atoms which may have a substituent, a carboxyl group, an aldehyde group, a hydroxyl group, a halogen atom,
Or represents a hydrogen atom. ) 7. The binder resin according to the following general formula (II)
7. The electrophotographic photoreceptor according to claim 6, wherein the polyester resin represented by I) is contained in an amount of 5% by weight or more and 50% by weight or less based on the total amount of the binder resin. Embedded image (Where g, h and i are integers from 1 to 10, v, w,
x and y represent an integer of 10 to 1000. ) 8. The electrophotographic photoreceptor according to claim 7, wherein the weight ratio of the polycarbonate resin / the polyester resin is in a range of 9/1 to 7/3. 9. The photosensitive layer contains α-tocopherol as an antioxidant, and the weight ratio of antioxidant / charge transfer material is 0.1 / 100 or more and 5/100 or less. 9. The electrophotographic photosensitive member according to any one of 1 to 8. 10. The photosensitive layer according to claim 2, wherein said antioxidant is 2,6.
-Di-t-butyl-4-methyl-phenol,
Antioxidant / charge transfer material weight ratio of 0.1 / 100
The ratio is not less than 50/100 and not more than 50/100.
9. The electrophotographic photoreceptor according to any one of items 1 to 8, 11. The method according to claim 1, wherein the surface layer contains dimethylpolysiloxane at a weight ratio of dimethylpolysiloxane / binder resin of 0.001 / 100 or more and 5/100 or less. The electrophotographic photoreceptor according to any one of the above.