JP2002333731A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor less susceptible to ozone and NOx generated from a system, having stable characteristics and image quality even after repeated use, having very high durability and usable in various printers, etc., as well as in an electrophotographic coping machine in a wide field of application of electrophotography. SOLUTION: The electrophotographic photoreceptor is obtained by stacking at least an electric charge generating layer containing an electric charge generating material and an electric charge transporting layer containing an electric charge transporting material in this order on an electrically conductive substrate. At least phthalocyanine is contained as the electric charge generating material in the electric charge generating layer, at least a diphenylamine compound and/or a triphenylamine compound is contained as the electric charge transporting material in the electric charge transporting layer and an amine compound having a specified structure is further contained in the electric charge transporting layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member. More specifically, the present invention relates to an electrophotographic photoreceptor having excellent ozone resistance, stability and durability, and an image forming apparatus using the photoreceptor.

[0002]

2. Description of the Related Art Selenium and selenium are known as electrophotographic photosensitive members.
Inorganic photoconductive materials such as tellurium alloys, arsenic selenide, and cadmium sulfide have been widely used, but in recent years, studies using organic photoconductive materials with low pollution and easy production for the photosensitive layer have been actively conducted. It has become. In particular, the mainstream is a laminated photoreceptor consisting of a charge generation layer and a charge transport layer, which separate the function of generating charge by absorbing light and the function of transporting the generated charge, such as copiers and laser printers. Widely used in the field. Such a laminated electrophotographic photoreceptor has a charge transport layer laminated on the charge generation layer,
Also, since the charge transport layer usually has only a hole transfer function,
It has sensitivity only when negatively charged, and is used under negative charging.

On the other hand, there has been proposed a so-called inverted two-layer type photoreceptor in which a charge transport layer and a charge generation layer are laminated on a support in this order, and a dispersion type photoreceptor in which particles of a charge generation substance are dispersed in a charge transport medium. Considerations are taking place. In the case of a reverse two-layer, dispersion type photoreceptor, incident light is absorbed on the surface, and a region where carriers are generated becomes near the surface, and is used by positive charging. As described above, photoconductors having several configurations have been proposed and studied, and photoconductors having excellent chargeability and sensitivity have been developed. However, the electrophotographic photoreceptor is used repeatedly in the system, and the electrophotographic photoreceptor is always required to have constant and stable electrophotographic characteristics, and such stability and durability are required in any structure. At present, enough things have not yet been obtained. That is, with repeated use, a decrease in the potential, a rise in the residual potential, a change in the sensitivity, etc., occur, and the copy quality deteriorates, making the product unusable. Not all of the causes of these deteriorations are known,
Several factors are possible. In particular, it has been found that oxidizing gases such as ozone and nitrogen oxides released from the corona discharge charger cause significant damage to the photosensitive layer. These oxidizing gases chemically change the material in the photosensitive layer and cause various changes in characteristics. For example, a decrease in charging potential,
An increase in the residual potential and a decrease in the resolution due to a decrease in the surface resistance are observed. On the other hand, the gas around the corona charger is efficiently exhausted and replaced, and some measures are taken to avoid the influence on the photoreceptor.
It has been proposed to add a stabilizer to prevent deterioration. For example, JP-A-62-105151 discloses the addition of an antioxidant having a triazine ring and a hindered phenol skeleton in the molecule, and JP-A-63-18355 describes the addition of a specific hindered amine. JP-A-63-4238,
JP-A-63-216055 describes the addition of trialkylamines and aromatic amines.

Japanese Patent Application Laid-Open No. 3-172852 discloses an electrophotography using phthalocyanine as a charge generating substance, using a hydrazone compound as a charge transporting substance, and further comprising a charge transporting layer containing an amine compound such as tribenzylamine. A photoreceptor is described. JP-A-7-24438
No. 9 discloses an electrophotographic photoreceptor using phthalocyanine for the charge generation layer, an arylamine compound for the charge transport layer, and an aniline compound or phenylenediamine compound for the charge generation layer as an antioxidant. Is described.

Japanese Patent Application Laid-Open No. 8-292587 discloses that phthalocyanine may be used for the charge generation layer, an arylamine compound is used for the charge transport layer, and tribenzylamine or the like is used for the charge generation layer as an antioxidant. The use of an amine compound is described. JP-A-10-2826
No. 96, oxytitanium phthalocyanine is used for the charge generation layer, a hydrazone compound is used for the charge transport layer, and an amine compound such as tribenzylamine and a hindered amine or hindered amide compound are used for the charge transport layer as an antioxidant. The electrophotographic photosensitive member used is described.

JP-A-9-244278 describes an electrophotographic photoreceptor using oxytitanium phthalocyanine as a charge-generating substance and an arylamine-based compound as a charge-transporting substance.

[0007]

However, even with these conventional techniques, a sufficient ozone resistance effect has not yet been obtained, or electrophotographic characteristics such as sensitivity and residual potential have been reduced by the addition of such an antioxidant. At present, only sufficient effects for practical use, such as worsening, were obtained.

[0008] Although the use environment of the copier and the laser printer is various, depending on the case, the copier and the laser printer are sometimes used in an acidic gas atmosphere. A photoreceptor having stable performance even under such an environment is desired.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies on the improvement of ozone resistance and acid gas resistance of an organic photoreceptor having a charge generating substance and a charge transport substance.
By adding a specific amine compound to the photosensitive layer,
The present inventors have found that a photoreceptor having remarkably improved ozone resistance and acid gas resistance and having excellent electric characteristics can be obtained, thereby completing the present invention.

That is, the gist of the present invention is that a conductive support is
An electrophotographic photosensitive member in which a charge generation layer containing at least a charge generation material and a charge transport layer containing a charge transport material are laminated in this order, wherein the charge generation layer contains at least phthalocyanine as a charge generation material. The charge transport layer contains at least one or both of a diphenylamine compound and a triphenylamine compound as a charge transport material, and the charge transport layer further contains an amine compound having the following general formula (1). Electrophotographic photoreceptor.

[0011]

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(Wherein A and B each represent an aromatic ring residue, an aromatic heterocyclic residue, an aralkyl group, a cycloalkyl group, or a heterocycloalkyl group, each of which has a substituent. R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group, and the alkyl group, cycloalkyl group and aralkyl group may have a substituent.)

Hereinafter, the present invention will be described in detail. The photosensitive layer of the present invention has a charge generation layer containing at least phthalocyanine as a charge generation material on a conductive support, and a charge transport layer containing at least one or both of a diphenylamine compound and a triphenylamine compound as a charge transport material. A configuration such as a laminated photoreceptor laminated in this order is an example of a basic form.

These photosensitive layers are formed on a conductive support by a known method such as roll coating, bar coating, dip coating, spray coating and the like. If necessary, between the conductive support and the photosensitive layer, an anodic oxide film represented by an alumite layer, or a polyamide resin, an undercoat layer made of a copolymerized polyamide resin,
Alternatively, an undercoat layer in which aluminum oxide particles; titanium oxide particles; titanium oxide particles coated with a polysiloxane, a silane compound or the like are dispersed in these resins may be provided. Further, an undercoat layer may be formed on the anodic oxide film. A protective layer made of a polyamide resin, a thermosetting silicone resin, a crosslinked acrylic resin, or the like may be provided on the surface of the photosensitive layer as needed.

Various known conductive supports can be used. For example, aluminum, aluminum alloy,
Metal drums of copper, nickel, stainless steel, etc .; Laminated metal foil, deposited or sputtered metal, conductive oxide, etc., or conductive materials such as metal powder, carbon black, copper iodide, tin oxide Plastic films, plastic drums, glass drums, paper, etc., which have been subjected to a conductive treatment such as coating with a binder resin as necessary.

As the charge generating substance used in the present invention,
A phthalocyanine represented by the following general formula can be exemplified.

[0017]

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(Where M is Cu, Fe, Mg, Si,
Metal atoms such as Ge, Sn, and Pb, InCl, GaCl,
AlCl, TiO, SnCl_Two, Sn (OH)_Two, Si
(OH) _TwoOr two hydrogen atoms.
X is a C1-C4 alkyl group, a C1-C4 alkoxy
Group, nitro group, cyano group, halogen atom, etc.
Represents an integer of 0 to 4. Of these, M is InCl, GaCl, AlC
1, TiO, SnCl _Two, Sn (OH)_Two, Si (OH)
_TwoOr phthalo which is two hydrogen atoms
Preference is given to cyanine, GaCl, AlCl, TiO, S
nCl_TwoMore preferably two hydrogen atoms, Cu
In X-ray diffraction by Kα ray, Bragg angle (2θ ± 0.
2 degrees) Diffraction peaks at 9.7 degrees, 24.2 degrees and 27.3 degrees
Titanyloxyphthalocyanine and Bragg angle
(2θ ± 0.2 degrees) 9.3 degrees, 10.6 degrees, 13.2
Degrees, 15.1 degrees, 15.7 degrees, 16.1 degrees, 20.8
Degrees, 23.3 degrees, 26.3 degrees and 27.1 degrees
Oxytitanium phthalocyanine, which shows
No. The above phthalocyanines may be used alone or as a mixture of two or more.
And may be used in combination with other charge generating substances.
No.

It has been found that in the combination of phthalocyanine and the amine compound used in the present invention, the deterioration of electrophotographic characteristics such as sensitivity and residual potential due to the addition of the amine compound is smaller than the combination of the azo compound and the amine compound. . In this case, the amine compound is added to the charge transport layer, which seems strange at first glance. However, when the charge transport layer is coated on the charge generation layer, it is known that the substance in the charge transport layer penetrates from the charge transport layer into the charge generation layer, and the soaked amine compound It is considered that phthalocyanine has good compatibility.

The charge generating substance is used as a main component of the charge generating layer, and may be used as a uniform layer formed by a method such as vapor deposition or sputtering, or dispersed in a binder resin in the form of fine particles. It may be used in such a form. In this case, as the binder resin, polyvinyl acetate, polyacrylate, methacrylate resin, polyester resin, polycarbonate resin, polyvinyl butyral, polyvinyl acetal resin such as polyvinyl formal, phenoxy resin, cellulose ester, cellulose ether, urethane resin, epoxy resin, etc. Various binder resins can be used. The composition ratio of the charge generating substance to the binder resin is usually 100: 10 to 5: 100 by weight.
And a charge transport material may be mixed in this layer. The thickness of the charge generation layer is usually 0.1 to 10 μm.
Preferably, m is used.

The charge transport material used in the present invention is preferably a diphenylamine compound or a triphenylamine compound, and more preferably a diphenylamine compound or a triphenylamine compound represented by the following general formula (2). Used.

[0022]

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In the general formula (2), P represents a hydrogen atom or a group represented by the following general formula (3);

[0024]

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Q ¹ and Q ² are alkyl groups such as methyl group, ethyl group and propyl group; aryl groups such as phenyl group, naphthyl group and anthracenyl group; aralkyl groups such as benzyl group and phenethyl group; pyrrolyl group and thienyl And a heterocyclic group such as a furyl group. These alkyl groups, aryl groups, and heterocyclic groups may have one or more substituents. Examples of the substituent include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; an alkyl group such as a methyl group, an ethyl group and a propyl group; an alkoxy group such as a methoxy group, an ethoxy group and a propyloxy group; a phenyl group and a naphthyl group An aryl group; a dialkylamino group such as a diethylamino group;
Diarylamino group such as diphenylamino group; diaralkylamino group such as dibenzylamino group; diheterocyclic amino group such as dipyridylamino group; divinylamino group; diallylamino group; It represents a substituted amino group such as a disubstituted amino group, and the substituent is particularly preferably a hydrogen atom, a methyl group, a methoxy group, or a phenyl group. Q ¹ and Q ² are particularly preferably phenyl, tolyl, xylyl and naphthyl. When Q ¹ and Q ² have two or more substituents, these substituents may be linked directly or via a bonding group. As the bonding group, a methylene group,
Examples thereof include an alkylene group such as an ethylene group and a trimethylene group.

R ² and R ² ′ and R ³ and R ³ ′ represent a chlorine atom,
A halogen atom such as a bromine atom and an iodine atom; an alkyl group such as a methyl group, an ethyl group and a propyl group; an alkoxy group such as a methoxy group, an ethoxy group and a propyloxy group; an aryl group such as a phenyl group and a naphthyl group; Aralkyl groups such as phenethyl group; dialkylamino groups such as diethylamino group; diarylamino groups such as diphenylamino group; diaralkylamino groups such as dibenzylamino group; diheterocyclic amino groups such as dipyridylamino group; divinylamino group; A diallylamino group; a substituted amino group such as a di-substituted amino group obtained by combining the above-mentioned amino group substituents, which may be the same or different, and a methyl group and a methoxy group are particularly preferable. These alkyl group, alkoxy group, aralkyl group, and aryl group may have a substituent, and the substituent includes a chlorine atom,
Halogen atom such as bromine atom and iodine atom; alkyl group such as methyl group, ethyl group and propyl group, alkoxy group such as methoxy group, ethoxy group and propyloxy group; vinyl group; allyl group; benzyl group and phenethyl group Aralkyl group; aryloxy group such as phenoxy group and toloxy group; arylalkoxy group such as benzyloxy group and phenethyloxy group; aryl group such as phenyl group and naphthyl group; arylvinyl group such as styryl group and naphthylvinyl group; An acyl group such as a benzoyl group; a dialkylamino group such as a diethylamino group; a diarylamino group such as a diphenylamino group; a diaralkylamino group such as a dibenzylamino group; a diheterocyclic amino group such as a dipyridylamino group; A diamine obtained by combining a substituent of the above amino group; And a substituted amino group such as a substituted amino group. These substituents are condensed with each other to form a carbon ring group via a single bond, a methylene group, an ethylene group, a carbonyl group, a propenylene group, a vinylene group, or the like; A heterocyclic group containing an atom, a sulfur atom, a nitrogen atom and the like may be formed.
And l, l ', m, m' represent an integer of 0 to 4;
h represents an integer of 0 to 3. l, l ', m, m' are 0
And an integer of from 2 to 2 is preferred. n and h are preferably integers of 0 to 2.

R ⁴ , R ⁴ ′, R ⁵ , R ⁵ ′ and R ⁶ , R ⁶ ′
Each represents a hydrogen atom; an alkyl group such as a methyl group, an ethyl group or a propyl group; an alkoxy group such as a methoxy group or an ethoxy group; an aryl group such as a phenyl group or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group; Represents a heterocyclic group such as a pyrrolyl group, a thienyl group, and a furyl group, which may be the same or different from each other; A heterocyclic group is
Particularly, a heterocyclic group having aromaticity is preferable. These alkyl group, alkoxy group, aryl group, aralkyl group, and heterocyclic group may have a substituent, and examples of the substituent include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; a methyl group and an ethyl group. An alkyl group such as a propyl group, a methoxy group, an ethoxy group, an alkoxy group such as a propyloxy group;
Vinyl group; allyl group; aralkyl group such as benzyl group and phenethyl group; aryloxy group such as phenoxy group and toloxy group; arylalkoxy group such as benzyloxy group and phenethyloxy group; aryl group such as phenyl group and naphthyl group; Aryl vinyl groups such as styryl group and naphthyl vinyl group; acyl groups such as acetyl group and benzoyl group;
A dialkylamino group such as a diethylamino group; a diarylamino group such as a diphenylamino group; a diaralkylamino group such as a dibenzylamino group; a diheterocyclic amino group such as a dipyridylamino group; a diallylamino group; Substituted amino groups such as a di-substituted amino group in which the groups are combined, and these substituents are condensed with each other to form a single bond, a methylene group, an ethylene group, a carbonyl group,
A carbon ring group via a propenylene group, a vinylene group, or the like; a heterocyclic group containing an oxygen atom, a sulfur atom, a nitrogen atom, or the like may be formed. When n and h = 2 or 3, R ⁴ and R ⁵ and R ⁴ ′ and R ⁵ ′ may be the same or different, or R ⁵ and R ⁶ and R ⁵ ′ and R ⁶ A pair consisting of a carbocyclic group condensed to form a single bond, a methylene group, an ethylene group, a carbonyl group, a propenylene group, a vinylene group, etc .;
A heterocyclic group containing an oxygen atom, a sulfur atom, a nitrogen atom and the like may be formed. Q ¹ and R ³ , Q ² and R ³ ′, Q ¹ and R ⁶ , Q ² and R
⁶ ′ may be condensed with each other to form a single bond, a methylene group, an ethylene group, a propenylene group, a vinylene group, a carbocyclic group or a heterocyclic group via a carbonyl group, or an oxygen atom, a sulfur atom Or a heterocyclic group via a nitrogen atom.

In the diphenylamine-based compound or triphenylamine-based compound used in the present invention, the diphenylamine or triphenylamine units are directly bonded to each other as represented by the general formulas (2) and (3). . This is because the spread of the conjugated system is considered to be important for the charge transport ability. For example, if a methylene chain such as a methylene group, an ethylene group or a propylene group or a hetero atom such as an oxygen atom or a sulfur atom is present as a linking group in a portion connecting diphenylamine or triphenylamine units, the conjugation is impaired. This increases the residual potential and the like. Therefore, a linking group having no methylene chain, oxygen atom, sulfur atom or the like is preferable. In fact, when a charge transporting substance such as Compound Example A-12 or A-15 of JP-A-8-292587 is used, a high residual potential has been observed.

Representative examples of the arylamine-based compound represented by the general formula (2) will be given below. These representative examples are shown for illustrative purposes, and the arylamine-based compound used in the present invention is: It is not limited to these representative examples.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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As the binder resin used together with the charge transporting material, various known resins can be used. Thermoplastic resins and curable resins such as polycarbonate resins, polyester resins, polyarylate resins, acrylic resins, methacrylate resins, styrene resins, and silicone resins can be used. Particularly, a polycarbonate resin, a polyacrylate resin, and a polyester resin, which cause less abrasion and damage, are preferable. Polycarbonate resin contains bisphenol A, bisphenol C, bisphenol P, bisphenol Z, or
Various known components can be used. Further, a copolymer composed of these components may be used.

The charge transporting material and the binder resin are compounded in an amount of, for example, 10 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the resin. In the case of a laminated photoreceptor, the charge transporting layer is formed mainly of the above components, and the thickness of the charge transporting layer is usually 5 to 50 μm, preferably 10 to 40 μm. The amine compound used in the present invention is a compound represented by the following general formula (1) as described above.

[0037]

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(Where A and B each independently represent an aromatic ring such as a phenyl group, a naphthyl group or an anthracenyl group; an aromatic heterocyclic ring such as a thiophenyl group; an aralkyl group such as a benzyl group or a phenethyl group; a cyclohexyl group Or a heterocycloalkyl group such as tetrahydrofuranyl, and these groups may further have a substituent such as an alkyl group, an aryl group, an aralkyl group, etc. A and B are phenyl Is preferred.

R ¹ is a hydrogen atom; a methyl group, an ethyl group,
An alkyl group such as a propyl group or a t-butyl group; a cycloalkyl group such as a cyclohexyl group; or an aralkyl group such as a benzyl group or a phenethyl group, wherein the alkyl group, the cycloalkyl group, and the aralkyl group are a hydroxyl group, an alkoxy group, It may have a substituent such as a cyano group, a heterocyclic residue or a halogen atom. R ¹ is more preferably when the hydrogen atom, a benzyl group, especially a benzyl group is preferable as R ^1. Hereinafter, typical examples of the amine compound represented by the general formula (1) will be described. However, these typical examples are shown for illustrative purposes, and the compounds used in the present invention are not limited to these typical examples. is not.

[0040]

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As described above, these amine compounds are added to the charge transport layer. For example, when the charge transport layer is formed by a dip coating method or the like, the amine compound is charged during the coating under the charge transport layer. It also enters the generating layer.
Therefore, it is considered that compatibility with the charge generation material occurs as in the present invention. When a protective layer or undercoat layer is provided, it is added to these protective layers or undercoat layers as needed. The amount of the amine compound to be added is usually 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, in the layer.

In the present invention, a known antioxidant may be added, and as such an antioxidant, a hindered phenol-based antioxidant is preferable.
As the hindered phenolic antioxidant,
3,5-di-tert-butyl and 4-hydroxytoluene are preferred. Further, the photosensitive layer of the present invention has a known plasticizer for improving film formability, flexibility, mechanical strength, etc., an additive for suppressing accumulation of residual potential, and a dispersion for improving dispersion stability. An auxiliary agent and a leveling agent for improving applicability, for example, silicone oil and other additives may be added.

The image forming apparatus of the present invention includes a monochrome printer, a copying machine, a color printer, a color copying machine, a facsimile, and the like. In the image forming apparatus of the present invention, the effect of the present invention can be usually obtained by using a light source such as a laser beam having a conventionally known wavelength range, but a light source having a wavelength range of 380 nm to 600 nm. It is considered that the effect of the present invention can be achieved also in the image forming apparatus using the image forming apparatus.

The image forming apparatus includes a charging unit for uniformly charging the photosensitive member, and then exposing the photosensitive member to an image to dissipate the charge of the exposed portion to form an electrostatic latent image. Unit, a developing unit that visualizes and develops the electrostatic latent image by attaching charged toner, a transfer unit that transfers the obtained visible image to a transfer material such as transfer paper, heating, pressing, etc. A fixing unit for fixing the visible image to the transfer material and a cleaning unit for removing toner remaining on the surface of the photoconductor after transferring the toner to the transfer material are provided. In some cases, a charge elimination unit is provided to remove charges remaining on the surface of the photoconductor after cleaning. Further, a transport unit that transports the recording medium (paper) is provided.

In the image forming apparatus of the present invention, a non-contact charger such as a corona charger represented by a corotron or a scorotron; a contact charger such as a charging roller or a charging brush is used as a charger. Exposure: halogen lamp, fluorescent lamp, laser (semiconductor, He-Ne), LED
Using a light source such as, the normal exposure method from the outside of the photoconductor,
This is performed by an exposure method or the like from the inside of the photoconductor. The development is performed by a dry development method such as a cascade development, a contact or non-contact development using a non-magnetic one-component toner, a contact or non-contact development using a magnetic one-component toner, a two-component magnetic brush development, a wet development method using a liquid toner, or the like. Done. The transfer is performed by an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, an adhesive transfer method, and the like, and the fixing is performed by heat roller fixing, flash fixing, oven fixing, pressure fixing, and the like. Cleaning is performed by brush cleaning, magnetic brush cleaning, electrostatic brush cleaning, magnetic roller cleaning, blade cleaning, or the like.

When performing full-color printing, the image forming apparatus transfers a developer such as a toner adhered on an electrophotographic photosensitive member to a single intermediate transfer belt once.
The color image may be formed on a recording medium (paper) by using a transfer unit after a toner of each color is combined to form a color visible image in an intermediate transfer belt shape.

[0047]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, “parts” means “parts by weight”. [Example 1] Titanium oxide (product name T, manufactured by Ishihara Sangyo Co., Ltd.)
TO-55N), and methylhydrogenpolysiloxane was uniformly applied to the surface at 3% by weight. Next, the obtained methyl hydrogen polysiloxane-treated titanium oxide and mixed alcohol (methanol / 1-propanol = 7 /
3) was dispersed in a ball mill for 16 hours. The titanium oxide dispersion obtained here was mixed with a mixed alcohol (methanol / methanol / random copolymer polyamide having the following structure manufactured by the manufacturing method described in Examples of JP-A-4-31870.
1-propanol = 70/30) solution, and finally a dispersion having a solid content concentration of 16% by weight with a titanium oxide / nylon ratio of 3/1 (weight ratio) was prepared. The resulting dispersion has a mirror-finished outer diameter of 30 mm, a length of 254 mm,
An aluminum cylinder having a thickness of 1.0 mm was applied by dip coating, and an undercoat layer was provided so that the dry film thickness was 0.75 μm.

[0048]

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In the X-ray diffraction spectrum, Bragg angle (2θ ± 0.2 degrees) 9.3 degrees, 10.6 degrees, 13.2 degrees
Degrees, 15.1 degrees, 15.7 degrees, 16.1 degrees, 20.8
Degree, 23.3 degrees, 26.3 degrees and 10 parts by weight of oxytitanium phthalocyanine having main diffraction peaks at 27.1 degrees are added to 150 parts by weight of 1,2-dimethoxyethane,
A pigment dispersion P was prepared by pulverizing and dispersing with a sand grind mill. Next, pigment dispersion liquid Q was prepared in exactly the same manner for oxytitanium phthalocyanine having a main diffraction peak at a Bragg angle (2θ ± 0.2 degrees) of 27.3 degrees in the X-ray diffraction spectrum. 80 parts by weight of the pigment dispersion P thus prepared and 80 parts by weight of the pigment dispersion Q were mixed to obtain 160 parts by weight.
5 parts by weight of polyvinyl butyral (trade name # 6000-C, manufactured by Denki Kagaku Kogyo KK)
In addition to 100 parts by weight of the dimethoxyethane solution, a dispersion R having a final solid content of 4.0% was prepared. An aluminum cylinder provided with an undercoat layer was dip-coated on the dispersion to give a dry film thickness of 0.3 g / m ² (about 0.3 μm).
m) The charge generation layer was provided.

Next, this aluminum cylinder was
40 parts by weight of the arylamine compound shown in Compound Example (2-17), 1 part by weight of tribenzylamine, 3,5-di-t-butyl, 4-hydroxytoluene (hereinafter referred to as BHT) which is a known antioxidant 8 parts by weight) and 0.05 parts by weight of the following cyano compound:

[0051]

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100 parts by weight of the following polycarbonate resin (monomer molar ratio: 1: 1) having two repeating structural units, which is produced by the production method described in Examples of JP-A-3-221962.

[0053]

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The above-mentioned aluminum cylinder provided with an undercoat layer and a charge generation layer is dip-coated in a solution in which 1,4-dioxane and tetrahydrofuran are dissolved to obtain a dry film thickness of 22 μm. Was provided with a charge transport layer. The drum thus obtained is referred to as a photoconductor A1.

Comparative Example 1 A photoconductor B1 was produced in the same manner as in Example 1 except that tribenzylamine was not used.

The ozone resistance of the photoreceptor was measured by using an ozone generator manufactured by Ebara Corporation to reduce the ozone concentration to about 100 ppm.
The photosensitive drum produced as described above is exposed for 12 hours in a hermetically sealable container, and then stored in a room for one day, and the charged potential is measured before ozone exposure and after standing for one day after exposure. I checked by doing. That is, before exposure, the charging potential was set to a standard value, left for one day after exposure, and then measured again to determine the relative value as ozone resistance.

For the measurement of the electric characteristics of the present invention, an electric characteristic measuring device (manufactured by Mitsubishi Chemical Corporation) having a function of imitating the neutralization, charging and exposure processes of an actual electrophotographic apparatus was used.
Although this apparatus does not have the development, transfer, and cleaning processes of an actual electrophotographic apparatus, it is possible to measure the surface potential of the photoconductor at the development position of the actual electrophotographic apparatus. In the examples and comparative examples of the present invention, the electrical characteristics were measured under the condition that the photoconductor rotated 56 times per minute.

Table 1 shows the measurement results of the electrical characteristics.

[0059]

[Table 1]

The sensitivities in the table are as follows.
The relative sensitivity was set to 00 (= sensitivity of B1 / sensitivity of the photoconductor to be compared). According to Table 1, the photoreceptor of Example 1 has improved ozone resistance as compared with the system containing no amine.
The difference is slight.

Example 2 In the same manner as in Example 1, an undercoat layer and a charge generation layer were provided on an aluminum cylinder. Next, the aluminum cylinder was placed in the arylamine compound 70 shown in Compound Example (2-12).
100 parts by weight, 1 part by weight of tribenzylamine, 16 parts by weight of BHT, 1 part by weight of the same cyano compound used in Example 1 and 100 parts of the same polycarbonate resin (monomer molar ratio 1: 1) used in Example 1 The aluminum cylinder provided with the undercoating layer and the charge generation layer is dip-coated in a solution obtained by dissolving parts by weight in a mixed solvent of 1,4 dioxane and tetrahydrofuran so that the dry film thickness becomes 22 μm. A charge transport layer was provided. The drum thus obtained is referred to as a photoconductor A2. Comparative Example 2 A photoconductor B2 was produced in the same manner as in Example 2, except that tribenzylamine was not used.

[0062]

[Table 2]

As shown in Table 2, the photoreceptor of Example 2 has improved ozone resistance as compared with the system containing no amine system, but the difference is still slight.

The acid resistance of the photoreceptor was measured as follows. First, in the room of 20 ℃, 300cc
Pour 50 ml of concentrated hydrochloric acid into a beaker, and leave the beaker in a sealable container for several hours to create an atmosphere of hydrochloric acid gas of about 100 ppm. Next, the photoreceptor drum produced as described above was exposed for 15 hours, and the charging potential was measured before and after exposure to hydrochloric acid gas. That is, the charging potential was set to a standard value before the exposure, and the measurement was performed again after the exposure, so that the relative value was regarded as the acid gas resistance as in the ozone resistance.

[0065]

[Table 3]

As is clear from the results shown in Table 3, the photoreceptor A1 of Example 1 and the photoreceptor A2 of Example 2 using the amine compound of the present invention exhibited excellent acid-resistant gas characteristics.

Comparative Example 3 In the same manner as in Example 1, an undercoat layer and a charge generation layer were provided on an aluminum cylinder. Next, 70 parts by weight of a hydrazone compound having the following structural formula, 1 part by weight of tribenzylamine, 16 parts by weight of BHT, 1 part by weight of the same cyano compound as used in Example 1, and 1 part by weight of this aluminum cylinder were prepared. The above aluminum cylinder provided with an undercoat layer and a charge generation layer was placed in a solution in which 100 parts by weight of the same polycarbonate resin (monomer molar ratio: 1: 1) used in 1 was dissolved in a mixed solvent of 1,4 dioxane and tetrahydrofuran. The charge transport layer was provided by dip coating so that the dry film thickness became 22 μm. The drum thus obtained is referred to as a photoconductor B3.

[0068]

Embedded image

The photosensitive members of Examples 1 and 2 and Comparative Example 3 were charged to -600 V by the above-mentioned electrical property measuring apparatus, and then exposed to light intensity of 1 mJ / cm ² , and the surface potential was further increased by 1 mJ / cm ^2. The residual potential after rotation was measured. Table 5 shows the results. The photoconductors A1 and A2 of the present invention show better characteristics than the photoconductor B3 of the comparative example.

[0070]

[Table 4]

The photoreceptor A1 was rotated under the conditions that the photoreceptor was rotated 56 times per minute by using the above-mentioned electric characteristic measuring apparatus.
It exhibited stable chargeability and sensitivity even after 60,000 repetitions of charging and discharging. Further, the photosensitive member A1 was mounted on a commercially available printer, for example, HP LaserJet 4+, and an image was formed. As a result, a good image was obtained. based on the above results,
It can be seen that the photoreceptor of the present invention has very excellent performance.

[0072]

The electrophotographic photoreceptor of the present invention has excellent electrophotographic properties, is hardly affected by ozone and nitrogen oxides generated from the system, and is stable even in an acidic gas atmosphere or repeated use. It has the advantage of being a photoreceptor having extremely high durability with excellent characteristics and image quality.

The photoreceptor of the present invention can be used in a wide range of electrophotographic applications such as various printers, in addition to electrophotographic copying machines.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masayuki Hiroi 1060 Narita, Odawara-shi, Kanagawa F-term (reference) 2H068 AA14 AA16 AA19 AA20 AA37 BA12 BA13 BA14 BA39

Claims (5)

[Claims] 1. An electrophotographic photoreceptor comprising a charge generating layer containing at least a charge generating substance and a charge transporting layer containing a charge transporting substance laminated on a conductive support in this order. The layer contains at least phthalocyanine as a charge generating substance, the charge transport layer contains at least one or both of a diphenylamine compound and a triphenylamine compound as a charge transport substance, and the charge transport layer has the following general formula: An electrophotographic photoreceptor comprising an amine compound having the same. Embedded image (Wherein, A and B each represent an aromatic ring, aromatic heterocyclic, aralkyl group, cycloalkyl group, or a heterocycloalkyl group, which may have a substituent group, R ¹ Represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group, and the alkyl group, cycloalkyl group and aralkyl group may have a substituent.) 2. The charge transport material is represented by the following general formula (2).
Characterized in that it is an arylamine-based compound
Item 2. The electrophotographic photosensitive member according to Item 1. Embedded image(Where P is a hydrogen atom or the following general formula (3)
Represents a group represented by the following:Q¹And Q^TwoIs an alkyl group which may have a substituent,
Aryl group which may have a substituent, may have a substituent
Aralkyl group or heterocyclic group which may have a substituent
R;^Two, R^Two'And R^Three, R^Three'Is a halogen source
Having a substituent, an alkyl group which may have a substituent,
Alkoxy group, aryl which may have a substituent
Group or substituted amino group, which are the same as each other
Or l; l ', m, m' are from 0 to
Represents an integer of 4; n and h represent an integer of 0 to 3
R;^Four, R^Four', R^Five, R^Five'And R⁶, R⁶'Is hydrogen
Atom, alkyl group which may have a substituent,
Optionally substituted alkoxy group, ant optionally substituted
A heterocyclic group which may have a substituent or a substituent,
These may be the same or different; or
R^FiveAnd R⁶And R^Five'And R⁶'Are fused to form a carbocycle
Or a heterocyclic group, provided that R ^Five
And R⁶And R^Five'And R⁶', One of which is water
When the element is an atom or an alkyl group, the other
A group or a heterocyclic group; n, h = 2 or 3
If each R^FourAnd R^Five And R^Four'And R^Five'Is the same
It may be different. ) 3. The charge generation material is oxytitanium phthalocyanine, and diffraction peaks at 9.7, 24.2 and 27.3 degrees in Bragg angles (2θ ± 0.2 degrees) by X-ray diffraction using CuKα radiation. 9.3 showing the titanyloxyphthalocyanine and Bragg angle (2θ ± 0.2 degrees)
Degrees, 10.6 degrees, 13.2 degrees, 15.1 degrees, 15.7
3. The electron according to claim 1, wherein the electron is one or both of oxytitanium phthalocyanine having diffraction peaks at degrees of 16.1, 20.8, 23.3, 26.3, and 27.1 degrees. 4. Photoreceptor. 4. The electron according to claim 1, wherein the charge transport layer contains both an amine compound having the general formula (1) and a hindered phenolic antioxidant. Photoreceptor. 5. An image forming apparatus using the electrophotographic photosensitive member according to claim 1.