JP5264321B2 - Electrophotographic photoreceptor and image forming apparatus having the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor excellent in durability even in long-term repeated use or in an oxidative gas, and capable of outputting a high-quality image without image degradation, and to provide an image forming apparatus with the photoreceptor. <P>SOLUTION: The electrophotographic photoreceptor includes a conductive support, and on the conductive support, a monolayer type photosensitive layer including at least a charge generating substance and a charge transporting substance, or a multilayer type photosensitive layer including a charge generating layer including a charge generating substance and a charge transporting layer including a charge transporting substance, are layered in this order, and is characterized in that the charge transporting layer of the monolayer type photosensitive layer or the multilayer type photosensitive layer contains a specified diamine compound and is used in an image forming apparatus with an exposure means for forming an electrostatic latent image by exposure using a semiconductor laser at an oscillation wavelength of 350 to 500 nm or a light emitting diode as the exposure light source. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an electrophotographic photoreceptor excellent in durability and image characteristics and an image forming apparatus provided with the same.

An electrophotographic photosensitive member (hereinafter also referred to as “photosensitive member”) used in an electrophotographic image forming apparatus (hereinafter also referred to as “electrophotographic device”) widely used in digital multifunction peripherals, printers, and the like is a conductive support. A photosensitive layer containing a photoconductive material is laminated thereon, and an inorganic photoconductive material such as selenium has been conventionally used as the photoconductive material.
However, in recent years, organic photoconductive materials have been widely used from the viewpoints of environmental aspects, manufacturing costs, freedom of material selection, and the like.
Photoconductors using organic photoconductive materials (hereinafter also referred to as “organic photoconductors”) can select materials corresponding to various exposure light sources from visible light to infrared light, can select materials without environmental pollution, It has advantages such as low manufacturing costs.
On the other hand, the disadvantages include weak mechanical strength and easy adhesion of foreign matter, poor chemical durability, and deterioration of electrostatic characteristics of the photoconductor and generation of scratches on the surface when printing many sheets. Can be mentioned.

  In the organic photoreceptor, a function-separated type photoreceptor in which a charge generation function and a charge transport function are respectively assigned to different substances is used. The functional separation type photoreceptor is a single-layer type photosensitive member provided with a photosensitive layer in which a charge generation material having a charge generation function and a charge transport material having a charge transport function are co-dispersed in a binder resin called a binder resin. And a laminated type photoreceptor having a photosensitive layer in which a charge generation layer in which a charge generation material is dispersed and a charge transport layer in which a charge transport material is dispersed are laminated.

Multilayer photoreceptors have the advantage that the photosensitive layer can be easily designed, and that a photoreceptor excellent in sensitivity and stability can be produced relatively easily, and occupies the mainstream of organic photoreceptors.
On the other hand, a single-layer type photoreceptor has a single photosensitive layer, and therefore has higher productivity than a laminated photoreceptor, can be manufactured at a low manufacturing cost, and is a harmful substance when charged. Since it can be used in a positive charging process in which ozone is not easily generated, it has been put into practical use.

The performance required for the photoreceptor in the image forming process includes (1) excellent electrical characteristics such as chargeability, charge retention ability, photosensitivity and responsiveness, and (2) characteristics due to environmental changes such as temperature and humidity. (3) Excellent wear resistance in repeated use, that is, excellent mechanical durability, and (4) The electrical characteristics of (1) are stable even after repeated use. And excellent electrical durability.
When the photosensitive layer is formed by coating, the coating solution is required to be physically and chemically stable in order to improve the production efficiency of the photoreceptor.

On the other hand, the electrophotographic apparatus is required to have high durability, and the durability of the physical properties of the photoreceptor, the electrical durability, and the mechanical durability are required to be improved.
Among these, the mechanical durability is affected by the film strength of the photosensitive layer that is the surface layer of the photoreceptor, that is, the printing durability. If the film strength of the photosensitive layer is low and the printing durability is not sufficient, the surface of the photosensitive layer is scraped off by repeated use and the film thickness of the photosensitive layer decreases, causing changes in characteristics such as a decrease in charging potential and an increase in residual potential. It is easy.

  In order to improve printing durability, a method of providing a protective layer in which a filler is dispersed on the outermost surface layer of the photoreceptor is employed. However, in this method, although the mechanical durability is improved by improving the printing durability, the electrical durability due to repeated fatigue due to corona discharge, the oxidization gas such as ozone and NOx generated by the discharge, and the exposure by exposure light. At present, the durability against physical properties such as decomposition and deterioration of the charge transport material contained in the body surface layer is not yet sufficient.

Although all causes of deterioration such as potential decrease, increase in residual potential, and change in sensitivity due to repeated use and generation of acidified gas have not been elucidated, several factors are conceivable.
For example, in an electrophotographic system (electrophotographic apparatus) using a non-contact charging method, the surface of the photoconductor is not worn by rubbing because it does not contact the photoconductor, and the surface of the photoconductor is not easily scratched, and is mechanically durable. It can be expected to extend the life of the photoreceptor. However, there is a disadvantage that ozone is generated more than the contact charging method, and the photoreceptor is significantly deteriorated by oxidizing gas.

Oxidizing gas chemically changes the material in the photosensitive layer to cause various property changes.
For example, a decrease in charging potential, an increase in residual potential, and a decrease in surface resistance result in a decrease in resolving power.As a result, image blur such as white spots and black belts are generated on the output image, and the image quality is significantly reduced. In addition, the life of the photoreceptor is shortened.
For this phenomenon, proposals to incorporate measures to efficiently exhaust and replace the gas around chargers such as corona chargers and avoid direct gas effects on the photoreceptor, and to prevent oxidation in the photosensitive layer Proposals have been made to prevent deterioration of the photoreceptor itself by adding an agent and a stabilizer.

However, in the former proposal, it is necessary to provide a new exhaust system in the image forming apparatus for exhausting the oxidizing gas, and there is a problem that the entire process and the process itself become complicated.
In the tandem method (development method using a plurality of photoconductors and overlaying images) used in recent color image formation, a plurality of peripheral processes are mounted on a plurality of photoconductor drums. In addition, the oxidizing gas concentration increases dramatically and tends to promote defects such as image blur.

The latter proposal includes, for example, a method of adding an antioxidant having a triazine ring and a hindered phenol skeleton in the molecule to the photosensitive layer (see JP-A-62-105151 (Patent Document 1)). ).
However, depending on the amount of antioxidant used, the residual potential increases remarkably, and the antioxidant itself is altered by reaction with nitrogen oxides during long-term use, losing its effect, and charge transport materials and charge generating materials. However, there is a problem that the original characteristics cannot be maintained and charging and sensitivity are remarkably lowered, and the current situation is not sufficient.

On the other hand, image forming apparatuses using organic photoreceptors are required to output high-definition digital images in response to the growing demand for image output terminals such as printers in recent years.
As an exposure light source adapted to such a digital recording system, for example, a small and inexpensive semiconductor laser or light emitting diode with high reliability is often used.
The oscillation wavelength of a semiconductor laser that is most often used at present is in the near infrared light region around 780 to 800 nm, and the oscillation wavelength of a typical light emitting diode is 740 nm.

Recently, violet to blue short wavelength lasers (blue semiconductor lasers) or light-emitting diodes having an oscillation wavelength of 400 to 500 nm have been developed and marketed as exposure light sources for digital recording systems.
In general, the spot diameter D of a laser beam (laser beam) converged on the surface of a photosensitive member is expressed by the following equation, where λ is the wavelength of the laser beam (laser beam oscillation wavelength) and NA is the lens numerical aperture. .
D = 1.22λ / NA
According to this equation, since the spot diameter D is proportional to the oscillation wavelength of the laser light, it can be seen that a laser having a short oscillation wavelength may be used to reduce the spot diameter D.
That is, it can be seen that if a short wavelength laser is used instead of the currently mainstream near-infrared semiconductor laser, higher resolution image quality can be realized.

Short-wavelength lasers have been greatly expected to improve the recording density of optical discs, but conventional photoconductors are not expected to be used as exposure light sources for image forming apparatuses because they do not exhibit sensitivity in the wavelength range. It was.
A charge that exhibits absorption even at a wavelength of 500 nm or less on a general laminated photoreceptor that has been practically used, that is, a photoreceptor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support. If the generating material is used, it should generally be sensitive to exposure of short wavelength lasers of 500 nm or less. However, since the charge transport layer actually absorbs at a wavelength of 500 nm or less, the exposure light of the short wavelength laser used as the exposure light source is absorbed before reaching the charge generation layer, and the multilayer photoreceptor is Sensitivity is not shown in certain wavelength range.

Therefore, a material for the charge transport layer having a transmittance capable of sufficiently transmitting the exposure light must be selected. The transmittance of the charge transport layer required at this time is 60% or more, preferably 80% or more.
The transmittance X is expressed by the ratio of the incident light at the oscillation wavelength as A1 and the transmitted light after passing through the charge transport layer as A2, as shown in the following equation.
X = A2 / A1 × 100

  In addition, since the photoconductor is exposed to high-intensity light with a uniform wavelength component in the short wavelength region, the charge transport material and the charge generation material are easily deteriorated in long-term use, and nitrogen oxides and antioxidants are used. Oxidation products generated by this reaction are colored and the light transmittance is lowered, so that sufficient exposure is not performed, sensitivity is significantly lowered, and high image quality cannot be maintained.

JP 62-105151 A

  The present invention provides an electrophotographic photosensitive member that is excellent in durability against repeated use over a long period of time and an oxidizing gas, and that can output a high-quality image without abnormal images, and an image forming apparatus including the same. This is the issue.

  The present inventor has found that the above-mentioned problems can be solved by adding a diamine compound having a specific structure to a single layer type photosensitive layer or the charge transport layer of the multilayer type photosensitive layer, and has completed the present invention.

Thus, according to the present invention, a single-layer photosensitive layer containing at least a charge generation material and a charge transport material, or a charge generation layer containing a charge generation material and a charge transport material are contained on a conductive support. A stacked photosensitive layer in which the charge transport layer is stacked in this order is stacked,
The charge transport layer of the single layer type photosensitive layer or the multilayer type photosensitive layer is represented by the general formula (I):

[Where:
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different and each may have an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent which may have 1 A valent heterocyclic residue;
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are the same or different and are a linear alkylene group which may have a substituent;
Z ^{is, I) -Ar 5 -, ii} ) -Ar 5 -Ar 6 - or ^{iii) -Ar 5 -W-Ar 6} -
(Wherein Ar ⁵ and Ar ⁶ are the same or different and are an arylene group which may have a substituent or a divalent heterocyclic residue which may have a substituent; W is an oxygen atom; A linear, branched or cyclic alkylene group which may have a sulfur atom or a substituent]
And is used in an image forming apparatus provided with an exposure means for forming an electrostatic latent image by exposure using a semiconductor laser or a light emitting diode having an oscillation wavelength of 350 to 500 nm as an exposure light source. An electrophotographic photosensitive member is provided.

According to the present invention, the electrophotographic photosensitive member described above, a charging means for charging the electrophotographic photosensitive member, and a semiconductor laser having an oscillation wavelength of 350 to 500 nm as an exposure light source for the charged electrophotographic photosensitive member. Alternatively, an exposure unit that performs exposure using a light emitting diode to form an electrostatic latent image, a developing unit that develops the electrostatic latent image formed by exposure to form a toner image, and the developed toner image At least a transfer means for transferring onto the recording material, a fixing means for fixing the transferred toner image on the recording material to form an image, and a cleaning means for removing and collecting the toner remaining on the electrophotographic photosensitive member An image forming apparatus is provided.
Furthermore, according to the present invention, a plurality of the above-described image forming apparatuses are arranged as a unit, and different color toner images are sequentially superimposed on a recording medium using different color toners for each of the plurality of image forming apparatuses. An image forming apparatus is also provided that forms a color image together.

According to the present invention, the diamine compound of the general formula (I) captures an oxidizing gas such as ozone or nitrogen oxide, and the adsorption of the oxidizing gas to the charge generation material and the charge transport material is effectively suppressed. Therefore, decomposition and deterioration of the material in the photosensitive layer can be suppressed even during long-term use.
That is, the diamine compound of the general formula (I) is resistant to reaction with an oxidizing gas and can maintain the function as an antioxidant for a long period of time, so that coloration due to alteration of the charge generation material and the charge transport material can be suppressed. In addition, since the diamine compound of the general formula (I) is not colored even in the oxidation product generated by the reaction with nitrogen oxides, it can maintain sufficient transparency of the photosensitive layer throughout its life, and light in the short wavelength region. Excellent performance can be secured. Accordingly, an electrophotographic photosensitive member capable of forming an image with excellent sharpness and no abnormal image without causing deterioration in resolution due to a decrease in charge, an increase in residual potential, a decrease in sensitivity, or a decrease in surface resistance over a long period of time. Can be provided.

  Therefore, according to the present invention, it is possible to realize high-quality image formation excellent in sharpness with a short-wavelength laser, and a high-sensitivity and high-life electrophotographic photosensitive member that does not cause image blurring or pause memory and the same. An image forming apparatus can be provided.

  Further, according to the present invention, in an image forming apparatus that emits more oxidizing gas, an electrophotographic photosensitive member capable of realizing high-quality image formation with higher gas resistance and a long-term stable effect. An image forming apparatus including the same can be provided.

  The photoreceptor of the present invention is a single layer type photosensitive layer containing at least a charge generation material and a charge transport material on a conductive support, or a charge generation layer containing a charge generation material and a charge transport material containing a charge transport material. A laminated photosensitive layer laminated with a transport layer in this order is laminated, and the single-layer photosensitive layer or the charge transport layer of the laminated photosensitive layer contains a diamine compound represented by the general formula (I) And an image forming apparatus including an exposure unit that forms an electrostatic latent image by exposure using a semiconductor laser or a light emitting diode having an oscillation wavelength of 350 to 500 nm as an exposure light source.

Among the diamine compounds of general formula (I), in terms of chemical stability such as decomposition or alteration as a chemical substance, easy availability of raw materials, ease of production and high yield, and production cost, etc. A diamine compound in which Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ^{6 in} formula (I) are linear alkylene groups, ie, sub-formula (II):

Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Y ⁵ , Y ⁶ and Z are as defined in general formula (I); l, m, n and p are the same or different. (It is an integer of 1 to 3)
The diamine compound shown by these is preferable.

Furthermore, a diamine compound in which Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ in the general formula (I) are methylene groups, that is, the sub-formula (III):

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ have the same definitions as in general formula (I)).
A diamine compound represented by is particularly preferred.

Each substituent in general formula (I), sub-formula (II), and sub-formula (III) is demonstrated.
Examples of the aryl group that may have a substituent of Ar ¹ , Ar ² , Ar ^3, and Ar ⁴ include, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 2 to 6 carbon atoms. Examples include a dialkylamino group and an aryl group which may be substituted with a halogen atom.
Specifically, phenyl group, o-tolyl group, 2,4-xylyl group, 4-methoxyphenyl group, 3-methoxy-4-methylphenyl group, t-butylphenyl group, 4-diethylaminophenyl group, 4- A chlorophenyl group, a 4-fluorophenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. are mentioned. Among these, a phenyl group, an o-tolyl group, a 4-methoxyphenyl group, a 1-naphthyl group, a 2-naphthyl group Is particularly preferred.

Examples of the cycloalkyl group which may have a substituent of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include a cycloalkyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.
Specific examples include a cyclohexyl group, a cyclopentyl group, a 4,4-dimethylcyclohexyl group, and among these, a cyclohexyl group is particularly preferable.

As the monovalent heterocyclic residue which may have a substituent of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ , for example, a monovalent complex which may be substituted with an alkyl group having 1 to 4 carbon atoms. A ring residue is mentioned.
Specific examples include a furyl group, a 4-methylfuryl group, a benzofuryl group, a benzothiophenyl group, a tetrahydrofuryl group, and a tetramethyltetrahydrofuryl group. Among these, a furyl group and a benzofuryl group are particularly preferable.

As the linear alkylene group which may have a substituent of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ , for example, it may be substituted with an alkyl group having 1 to 4 carbon atoms. Good alkylene groups are mentioned.
Specific examples include a methylene group, an ethylene group, a propylene group, and a 2,2-dimethylpropylene group. Among these, a methylene group and an ethylene group are particularly preferable.

Examples of the arylene group which may have a substituent for Ar ⁵ and Ar ⁶ in Z include an arylene group which may be substituted with an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. It is done.
Specific examples include p-phenylene group, m-phenylene group, methyl-p-phenylene group, methoxy-p-phenylene group, 1,4-naphthylene group, benzoxazolen group, biphenylylene group, and the like. Among them, p-phenylene group, m-phenylene group, methyl-p-phenylene group, methoxy-p-phenylene group and 1,4-naphthylene group are preferable, and p-phenylene group and 1,4-naphthylene group are particularly preferable. .

Examples of the divalent heterocyclic residue optionally having a substituent for Ar ⁵ and Ar ⁶ in Z include a 1,4-furandiyl group, a 1,4-thiophenediyl group, and a 2,5-benzofurandyl group. 2,5-benzoxazolediyl group and N-ethylcarbazole-3,6-diyl group.

Examples of the linear, branched or cyclic alkylene group which may have a substituent for W in Z include, for example, an alkylene which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl halide group. Group or a cycloalkylidene group.
Specifically, alkylene groups such as methylene group, ethylene group, propylene group, and 2,2-dimethylpropylene group; cyclohexane such as cyclohexylidenyl group, 4,4-dimethylcyclohexylidenyl group, and cyclopentylidenyl group. Examples thereof include alkylidene groups, and among these, a methylene group and an ethylene group are particularly preferable.

The substituents Ar ¹ , Ar ² , Ar ³ and Ar ⁴ in the sub-formula (III) are the same or different and may be a phenyl group or a cyclohexyl group, and Ar ⁵ is a phenylene group or biphenylene. A group is preferred.
Further, the substituents Ar ¹ , Ar ² , Ar ³ and Ar ⁴ in the sub-formula (III) are phenyl groups or 4-methoxyphenyl groups, or the substituents Ar ¹ and Ar ⁴ are 2,4-xylyl groups. And the substituents Ar ² and Ar ³ are preferably cyclohexyl groups.

Specific examples of the diamine compound of the present invention are shown in Table 1.
In the following Tables 1-1 to 1-6, substituents are represented by the following abbreviations.
-Me-: methylene group -Et-: ethylene group -Tr-: trimethylene group -Dm-: 2,2-dimethyltrimethylene group

  Among the diamine compounds of the present invention shown in Tables 1-1 to 1-6, Exemplified Compound Nos. 1, 2, 4, 8, 14, 22, 29, 38, 50, 53 and 57 are preferred. 1 and 2 are particularly preferable. 2 is more preferable.

  The diamine compound of the present invention can be produced by the method shown in the following reaction scheme. That is, by heating the amine compound represented by the general formula (IV) and the general formula (V) and the dihalogen compound represented by the general formula (VI) in the presence of an organic amine base, the yield can be easily increased. The target product can be produced with high purity.

[Reaction formula]

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Z are as defined in the general formula (1); X ¹ and X ² represent a halogen atom)
Examples of the halogen atom of X ¹ and X ² in the reaction formula include a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom and a bromine atom are particularly preferable from the viewpoint of ease of handling and reactivity.

The reaction of the above reaction formula can be carried out, for example, as follows.
The secondary amine compounds (IV) and (V) and the dihalogen compound (VI) are dissolved or dispersed in a solvent, an organic amine base is added thereto, and the mixture is heated and stirred. After completion of the reaction, the precipitate is filtered off and recrystallized in ethanol, methanol, ethyl acetate or the like alone or in a mixed solvent system, whereby the target product can be obtained easily and with high purity in high yield.

The solvent is not particularly limited as long as it is inert to the above reaction and can dissolve or disperse the reaction substrate and the organic amine base. Specifically, aromatic hydrocarbons such as toluene and xylene; ethers such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; amides such as N, N-dimethylformamide; dimethyl sulfoxide and the like Examples thereof include sulfoxides, and these can be used alone or as a mixed solvent.
In addition, the usage-amount of a solvent in particular is not restrict | limited, According to reaction conditions, such as the usage-amount of a reaction substrate, reaction temperature, and reaction time, the quantity which a reaction advances smoothly can be suitably set.
Examples of the organic amine base include N, N-diisopropylethylamine, N, N-dimethylaminopyridine, 1,4-diazabicycloundecene and the like.

The ratio of the secondary amine compounds (IV) and (V) to the dihalogen compound (VI) is not particularly limited.
For example, when obtaining a symmetrical compound, that is, when only one of the secondary amine compounds (IV) and (V) is used, 1 equivalent of the dihalogen compound (VI) is taken into consideration in view of the efficiency of the reaction. It is preferable to use about 2.0 to 2.3 equivalents of the secondary amine compound to be used.
In addition, when obtaining an asymmetric compound, that is, when both the secondary amine compounds (IV) and (V) are used, the reaction efficiency and the like are taken into consideration with respect to 1 equivalent of the dihalogen compound (VI). Each secondary amine compound is preferably used in an amount of about 1.0 to 1.2 equivalents, that is, about 2.0 to 2.4 equivalents in total of the secondary amine compounds (IV) and (V).

The use ratio of the dihalogen compound (VI) and the organic amine base is not particularly limited, but considering the efficiency of the reaction, the organic amine base is used in an amount of 2. with respect to 1 equivalent of the dihalogen compound (VI). It is preferable to use about 05 to 5.0 equivalents.
The heating temperature and reaction time are not particularly limited, but it is preferable to react at 60 to 120 ° C. for 2 to 8 hours, depending on the solvent used in consideration of the efficiency of the reaction.

The photoreceptor of the present invention will be specifically described with reference to the drawings.
1 to 3 are schematic cross-sectional views showing the structure of the main part of the photoreceptor of the present invention.
FIG. 1 and FIG. 2 are schematic cross-sectional views showing the configuration of the main part of a multilayer photoreceptor in which the photosensitive layer is a multilayer photosensitive layer (also referred to as “function-separated photosensitive layer”) composed of a charge generation layer and a charge transport layer. FIG. The photoreceptor of the present invention may have a reverse two-layered laminated structure in which a charge generating layer and a charge transporting layer are formed in reverse order, but the laminated type is preferred.
FIG. 3 is a schematic cross-sectional view showing the configuration of the main part of a single-layer type photoreceptor that is a single-layer type photosensitive layer having a single photosensitive layer.

1 has a charge generation layer 205 containing a charge generation material 202 and a charge transport containing a charge transport material 203 on the surface (outer peripheral surface) of a cylindrical conductive support 201 made of a conductive material. A laminated photosensitive layer 204 in which the layer 206 is laminated in this order is formed.
The photoconductor 102 in FIG. 2 includes a subbing layer (intermediate layer) 207 (to be described later) and a charge generating substance 202 on the surface (outer peripheral surface) of a cylindrical conductive support 201 made of a conductive material. A stacked photosensitive layer 204 in which a layer 205 and a charge transport layer 206 containing a charge transport material 203 are stacked in this order is formed in this order.
3 has a single-layer photosensitive layer 204 ′ containing a charge generation material 202 and a charge transport material 203 on the surface (outer peripheral surface) of a cylindrical conductive support 201 made of a conductive material. Is formed.

[Conductive support 201]
The conductive substrate 201 serves as an electrode for the photoreceptor and also functions as a support member for other layers.
The constituent material of the conductive support is not particularly limited as long as it is a material used in this field.
Specifically, metals and alloy materials such as aluminum, aluminum alloy, copper, brass, zinc, nickel, stainless steel, chromium, molybdenum, vanadium, indium, titanium, gold, platinum: polyethylene terephthalate, polyamide, polyester, polyoxy Conductive materials such as polymer materials such as methylene and polystyrene, laminates of metal foil on the surface of substrates made of hard paper, glass, etc., metal materials or alloy materials deposited, conductive polymers, tin oxide, indium oxide, etc. Examples include those obtained by depositing or coating a compound layer.

The shape of the conductive support is not limited to a cylindrical shape as shown in FIGS. 1 and 2, and may be a sheet shape, a columnar shape, an endless belt shape, or the like.
If necessary, the surface of the conductive support is subjected to irregular reflection treatment such as anodizing film treatment, surface treatment with chemicals, hot water, coloring treatment, and surface roughening within a range that does not affect the image quality. May be given.

  The irregular reflection treatment is particularly effective when the photoreceptor according to the present invention is used in an electrophotographic process using a laser as an exposure light source. That is, in the electrophotographic process using a laser as an exposure light source, the wavelength of the laser beam is uniform, so the laser beam reflected on the surface of the photoconductor and the laser beam reflected inside the photoconductor cause interference, Interference fringes due to this interference may appear in the image and cause image defects. Therefore, by performing irregular reflection processing on the surface of the conductive support, it is possible to prevent image defects due to interference of laser light having a uniform wavelength.

[Laminated Photosensitive Layer 204]
The laminated photosensitive layer 204 includes a charge generation layer 205 and a charge transport layer 206. As described above, by assigning the charge generation function and the charge transport function to separate layers, the optimum material constituting each layer can be independently selected.

[Charge generation layer 205]
The charge generation layer 205 is mainly composed of a charge generation material 202 having a charge generation capability of generating charges by absorbing irradiated light, and optionally contains a known additive and a binder resin (binder).

As the charge generation material 202, a compound used in this field can be used.
Specifically, an azo pigment (having a carbazole skeleton, a styryl stilbene skeleton, a triphenylamine skeleton, a dibenzothiophene skeleton, an oxadiazole skeleton, a fluorenone skeleton, a bis-stilbene skeleton, a distyryl oxadiazole skeleton, or a distyryl carbazole skeleton. , Monoazo pigments, bisazo pigments, trisazo pigments, etc.), perylene pigments (peryleneimide, perylene acid anhydride, etc.), polycyclic quinone pigments (quinacridone, anthraquinone, pyrenequinone, etc.), phthalocyanine pigments (metal phthalocyanine, no Metal phthalocyanines, halogenated metal-free phthalocyanines, etc.), indigo pigments (indigo, thioindigo, etc.), squarylium dyes, azurenium dyes, thiapyrylium dyes, pyrylium salts, triphenylmethane Organic pigments or dyes such as dyes, further selenium, inorganic materials such as amorphous silicon. These charge generating materials can be used alone or in combination of two or more.

Among these charge generation materials, metal-free phthalocyanine pigments, oxotitanyl phthalocyanine pigments, bisazo pigments containing a fluorene ring and a fluorenone ring, bisazo pigments composed of aromatic amines, and trisazo pigments are preferred because they have high charge generation ability. Crystalline oxo titanyl phthalocyanine showing a diffraction peak at a Bragg angle (2 ± 0.2 °) of 27.3 ° in the X-ray diffraction spectrum is particularly preferred because of its high sensitivity.
Among the charge generation materials, azo pigments, perylene pigments, and polycyclic quinone pigments are particularly preferable because they have high sensitivity characteristics in a wavelength region of 350 to 500 nm.

  The charge generation layer is a chemical sensitizer, an optical sensitizer, an antioxidant, an ultraviolet absorber, a dispersion stabilizer, a sensitizer, a leveling agent, a plasticizer, as long as the preferable characteristics of the present invention are not impaired. An appropriate amount of one or more known additives selected from fine particles of inorganic compounds or organic compounds may be contained. These additives may be contained in the charge transport layer 206 described later, or may be contained in both the charge generation layer 205 and the charge transport layer 206.

  The chemical sensitizer and the optical sensitizer improve the sensitivity of the photoreceptor, suppress an increase in residual potential and fatigue due to repeated use, and improve electrical durability.

  Examples of chemical sensitizers include acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, and 4-chloronaphthalic anhydride; cyano compounds such as tetracyanoethylene and terephthalmalondinitrile, 4-nitrobenzaldehyde, and the like. Aldehydes; anthraquinones such as anthraquinone and 1-nitroanthraquinone; polycyclic or heterocyclic nitro compounds such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitrofluorenone; diphenoquinone compounds Examples thereof include electron-withdrawing materials and those obtained by polymerizing these electron-withdrawing materials.

  Examples of the optical sensitizer include xanthene dyes, quinoline pigments, organic photoconductive compounds such as copper phthalocyanine, triphenylmethane dyes represented by methyl violet, crystal violet, knight blue and victoria blue; erythrosin, Acridine dyes typified by rhodamine B, rhodamine 3R, acridine orange and frapeosin; thiazine dyes typified by methylene blue and methylene green; oxazine dyes typified by capri blue and meldra blue; cyanine dyes; styryl dyes; Examples include pyrylium salt dyes and thiopyrylium salt dyes.

Antioxidants can maintain sensitivity stability over a long period of time.
Antioxidants include phenolic antioxidants such as hindered phenols such as 2,6-di-t-butyl-p-cresol (BHT), amine antioxidants such as hindered amines, vitamin E, hydroquinone, Examples include paraphenylenediamine, arylalkanes and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds, and these can be used alone or in combination of two or more.

Hindered phenols have been frequently used in the past, but their use is limited by the risk of carcinogens in addition to harmful effects such as the formation of oxidation products that cause coloring by reaction with oxidizing gases. Tend to be.
In addition, since many hindered amines are colored by reaction with an oxidizing gas, their use is limited.
Coloring in the short wavelength region in the present invention indicates a decrease in transmittance and concerns about the influence on the sensitivity. Therefore, the amount is preferably small.

Leveling agents and plasticizers can improve film formability, flexibility and surface smoothness.
Examples of the leveling agent include a silicone leveling agent.
Examples of the plasticizer include dibasic acid esters such as phthalate esters, fatty acid esters, phosphate esters, chlorinated paraffins, and epoxy type plasticizers.

  Fine particles of an inorganic compound or an organic compound can enhance mechanical strength and improve electrical characteristics. Examples of such fine particles include fine particles exemplified in an undercoat layer described later.

The charge generation layer can be formed by a known dry method and wet method.
Examples of the dry method include a method in which the charge generation material 202 is vacuum-deposited on the surface of the conductive support 201.
As the wet method, for example, a charge generation layer forming coating solution is prepared by dissolving or dispersing the charge generation material 202 and, if necessary, an additive and a binder resin in an appropriate organic solvent, and this coating solution is electrically conductively supported. An example is a method in which the organic solvent is removed by applying to the surface of the body 201 or the surface of the undercoat layer 207 formed on the conductive support 201 and then drying.

The binder resin can improve the mechanical strength and durability of the charge generation layer, the binding property between layers, and the like, and a resin having a binding property used in this field can be used.
Specifically, vinyl resins such as polymethyl methacrylate, polystyrene, polyvinyl chloride, polycarbonate, polyester, polyester carbonate, polysulfone, polyarylate, polyamide, methacrylic resin, acrylic resin, polyether, polyacrylamide, polyphenylene oxide, etc. Thermoplastic resin: Thermosetting resin such as phenoxy resin, epoxy resin, silicone resin, polyurethane, phenol resin, alkyd resin, melamine resin, phenoxy resin, polyvinyl butyral, polyvinyl formal, partially cross-linked products of these resins, these resins Copolymer resins containing two or more of the structural units contained in (vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, acrylo Tolyl - insulating resin such as styrene copolymer resin). These binder resins can be used alone or in combination of two or more.

Although content of binder resin is not specifically limited, Usually, it is about 50-1000 weight part with respect to 100 weight part of charge generating substances, Preferably it is 67-200 weight part.
When the content of the binder resin is less than 50 parts by weight, not only the film strength of the charge generation layer is lowered, but also the dispersibility of the charge generation material is lowered and coarse particles may be increased. For this reason, surface charges other than the portion to be erased by exposure are reduced, and there is a risk that image defects, particularly an image called black spots where toner adheres to a white background and minute black spots are formed, increase.
On the other hand, if the binder resin content exceeds 1000 parts by weight, the sensitivity of the photoreceptor may be lowered.

  Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, diphenylmethane, dimethoxybenzene, and dichlorobenzene; halogenated hydrocarbons such as dichloromethane, dichloroethane, and tetrachloropropane; tetrahydrofuran (THF) , Ethers such as dioxane, dibenzyl ether, dimethoxymethyl ether and 1,2-dimethoxyethane; ketones such as methyl ethyl ketone, cyclohexanone, acetophenone and isophorone; esters such as methyl benzoate, ethyl acetate and butyl acetate, diphenyl sulfide Sulfur-containing solvents such as: Fluorinated solvents such as hexafluoroisopropanol; non-protons such as N, N-dimethylformamide and N, N-dimethylacetamide Such as a polar solvent and the like, which may be used alone or as a mixed solvent. A mixed solvent obtained by adding alcohols, acetonitrile, or methyl ethyl ketone to such a solvent can also be used. Among these solvents, non-halogen organic solvents are preferably used in consideration of the global environment.

Prior to dissolving or dispersing the constituent materials in the resin solution, the charge generating material may be pre-ground.
The preliminary pulverization can be performed using, for example, a general pulverizer such as a ball mill, a sand mill, an attritor, a vibration mill, or an ultrasonic disperser.
The dissolution or dispersion of the constituent materials in the resin solution can be performed using, for example, a general disperser such as a paint shaker, a ball mill, or a sand mill. At this time, it is preferable to appropriately set the dispersion condition so that impurities are generated from the container and the members constituting the disperser due to wear and the like and are not mixed into the coating liquid.

The application method of the charge generation layer forming coating solution is a baker applicator method, a bar coater method, a casting method, a spin coating method, a roll method, a blade method or the like in the case of a sheet, and a spray method or a vertical ring method in the case of a drum. And a dip coating method.
The dip coating method is a method in which a layer is formed on the conductive support 201 by immersing the conductive support 201 in a coating tank filled with a coating solution and then pulling it up at a constant speed or a sequentially changing speed. . Since this method is relatively simple and excellent in terms of productivity and cost, it is widely used for manufacturing a photoreceptor. In addition, you may provide the coating liquid dispersion | distribution apparatus represented by the ultrasonic generator in order to stabilize the dispersibility of a coating liquid in the apparatus used for the dip coating method.

Although it will not specifically limit if the temperature in the drying process of a coating film is the temperature which can remove the used organic solvent, 50-140 degreeC is suitable and 80-130 degreeC is especially preferable.
When the drying temperature is less than 50 ° C., the drying time may be long. On the other hand, if the drying temperature exceeds 140 ° C., the electrical characteristics during repeated use of the photoreceptor may deteriorate and the resulting image may deteriorate.
The temperature conditions in the production of such a photosensitive layer are common not only in the photosensitive layer but also in the formation of layers such as an intermediate layer described later and other processes.

  The thickness of the charge generation layer is not particularly limited, but is preferably 0.05 to 5 μm, particularly preferably 0.1 to 1 μm. If the thickness of the charge generation layer is less than 0.05 μm, the light absorption efficiency may be reduced, and the sensitivity may be reduced. Conversely, if the thickness of the charge generation layer exceeds 5 μm, the charge inside the charge generation layer may be reduced. Transport becomes a rate-determining step in the process of erasing the charge on the surface of the photoreceptor, and there is a possibility that the sensitivity is lowered.

[Charge transport layer 206]
The charge transport layer 206 includes a charge transport material 203 having the ability to accept and transport charges generated by the charge generation material 202, a diamine compound represented by the general formula (I), and a binder resin (binder). Contains as a main component.

As the charge transport material 203, a compound used in this field can be used.
Specifically, poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, oxadiazole derivatives Imidazole derivatives, 9- (p-diethylaminostyryl) anthracene, 1,1-bis (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, pyrazoline derivatives, phenylhydrazones, hydrazone derivatives, triphenylamine series Electron donating substances such as compounds, tetraphenyldiamine compounds, triphenylmethane compounds, stilbene compounds, azine compounds having a 3-methyl-2-benzothiazoline ring;
Fluorenone derivatives, dibenzothiophene derivatives, indenothiophene derivatives, phenanthrenequinone derivatives, indenopyridine derivatives, thioxanthone derivatives, benzo [c] cinnoline derivatives, phenazine oxide derivatives, tetracyanoethylene, tetracyanoquinodimethane, promanyl, chloranil And electron accepting substances such as benzoquinone. These charge transport materials can be used alone or in combination of two or more.

Among these charge transport materials, an enamine styryl compound, triphenyl, which is not easily damaged in an ozone atmosphere, has a high charge transport capability and a hole transport capability, and provides high sensitivity even in a binder-rich state. Particularly preferred are amine derivatives and bisamine compounds.
In the photoreceptor of the present invention, it is desirable that the charge transport material is transmissive (not absorbing) to light having a wavelength of 350 to 500 nm, that is, the oscillation wavelength of the semiconductor laser to be used.
From such a viewpoint, among the above charge transport materials, arylamine-based and benzidine-based compounds are particularly preferable.

By containing the diamine compound represented by the general formula (I) in the charge transport layer, the photosensitive member is imparted with oxidation resistance gas resistance such as ozone resistance and nitrogen oxide resistance. This is because the diamine compound captures oxidizing gases such as ozone, nitrogen oxides, chlorine oxides and sulfur oxides, and effectively suppresses the adsorption of the oxidizing gases to the charge generating materials contained in the charge generating layer. This is probably because of this.
Therefore, the photoreceptor containing the diamine compound represented by the general formula (I) in the photosensitive layer has excellent electrophotographic characteristics, is not easily affected by ozone and nitrogen oxides generated from the system, and can be used repeatedly. It has stable characteristics and image quality and achieves extremely high durability.

Although content of the diamine compound shown by general formula (I) is not specifically limited, Usually, it is 0.1-20 weight part with respect to 100 weight part of charge transport substances, Preferably it is 0.5-10 weight part.
If the content of the diamine compound is less than 0.1 parts by weight, the effect may be extremely small.
On the other hand, when the content of the diamine compound exceeds 20 parts by weight, the relative amount ratio with respect to the charge transporting material is increased, and there is a possibility that adverse effects such as a decrease in sensitivity may occur.
The diamine compound may be used as a mixture with other antioxidants as long as the electrical properties are not impaired.

As the binder resin, one or more of the same binder resins as those contained in the charge generation layer can be used.
Among these resins, polycarbonate-based resins, polyarylate resins and polystyrene resins are photochemically stable, particularly excellent in compatibility with the diamine compound represented by the general formula (I), and have a volume resistance value. Is preferably 10 ¹³ Ω or more, excellent in electrical insulation, and excellent in film formability and potential characteristics.
In the photoconductor of the present invention, it is desirable that the binder resin be transmissive (not absorbing) to light in the oscillation wavelength of the semiconductor laser used, that is, in the wavelength region of 350 to 500 nm. Also from such a viewpoint, the above binder resin is particularly preferable.

Although content of binder resin is not specifically limited, Usually, it is about 120-300 weight part with respect to 100 weight part of charge transport substances, Preferably it is 160-250 weight part.
When the binder resin content is less than 120 parts by weight, the sensitivity characteristics are good, but the charging characteristics, the mechanical strength of the film, the image stability against ozone, NOx, etc. generated in the charging process (halftone whiteout) ), The printing durability becomes lower than when the binder resin ratio is high, and the wear amount of the photosensitive layer may increase.
On the other hand, if the content of the binder resin exceeds 300 parts by weight, the binder resin ratio increases and the mechanical strength is good, but the viscosity of the coating solution increases when the photosensitive layer is formed by the dip coating method. Therefore, there is a possibility that the coating speed is lowered and the productivity is remarkably deteriorated. Further, if the amount of the solvent in the coating solution is increased in order to suppress an increase in the viscosity of the coating solution, a brushing phenomenon occurs and the formed charge transport layer may become cloudy.

  The charge transport layer may contain an appropriate amount of the same additive as that contained in the charge generation layer, if necessary, within the range not impairing the effects of the present invention. In the case of a laminated photosensitive layer, these additives are preferably contained in the charge transport layer rather than the charge generation layer. Among the additives, the antioxidant is preferably contained in the charge transport layer that is easily affected by the oxidizing gas.

The addition amount of the antioxidant is preferably from 0.1 to 40 parts by weight, particularly preferably from 0.5 to 15 parts by weight, based on 100 parts by weight of the charge transport material.
If the added amount of the antioxidant is less than 0.1 parts by weight, there is a possibility that sufficient effects cannot be obtained for improving the stability of the coating solution and improving the durability of the photoreceptor. On the other hand, if the amount of the antioxidant added exceeds 40 parts by weight, the photoreceptor characteristics may be adversely affected.

The charge transport layer 206 is formed by dissolving or dispersing a charge transport material, a diamine compound represented by the general formula (I), a binder resin, and other additives as required in a suitable organic solvent. The coating solution is applied to the surface of the charge generation layer 205 and then dried to remove the organic solvent. More specifically, for example, a charge transport layer forming coating solution is prepared by dissolving or dispersing a charge transport substance and, if necessary, other additives in a resin solution obtained by dissolving a binder resin in an organic solvent. Prepare.
Other processes and conditions are in accordance with the formation of the charge generation layer.

  Although the film thickness of a charge transport layer is not specifically limited, 5-50 micrometers is preferable and 15-40 micrometers is especially preferable. If the thickness of the charge transport layer is less than 5 μm, the charge holding ability may be reduced. Conversely, if the thickness of the charge transport layer exceeds 50 μm, absorption or scattering of a short wavelength laser may occur in the photoreceptor layer. There is a possibility that the image becomes significantly large, sharpness is lowered and residual potential is increased, and image deterioration is significantly caused.

[Undercoat layer (also referred to as “intermediate layer”) 207]
The photoreceptor of the present invention preferably has an undercoat layer 207 between the conductive support 201 and the single-layer photosensitive layer 204 ′ or the laminated photosensitive layer 204 (see, for example, FIG. 2).
The undercoat layer has a function of preventing charge injection from the conductive support to the single-layer type photosensitive layer or the laminated type photosensitive layer. That is, the decrease in chargeability of the single-layer type photosensitive layer or the multilayer type photosensitive layer is suppressed, the decrease in surface charge other than the portion to be erased by exposure is suppressed, and the occurrence of image defects such as fog is prevented. In particular, during image formation by the reversal development process, it is possible to prevent the occurrence of image fogging called black spots in which minute black dots made of toner are formed on a white background portion.
In addition, the undercoat layer covering the surface of the conductive support reduces the degree of unevenness, which is a defect on the surface of the conductive support, and makes the surface uniform, thereby forming a single layer type photosensitive layer or a multilayer type photosensitive layer. The film property can be improved, and the adhesion (adhesiveness) between the conductive support and the single-layer type photosensitive layer or the multilayer type photosensitive layer can be improved.

  For the undercoat layer 207, for example, a resin material is dissolved in an appropriate solvent to prepare a coating solution for forming an undercoat layer, this coating solution is applied to the surface of the conductive support 201, and the organic solvent is removed by drying. Can be formed.

Examples of the resin material include natural polymer materials such as casein, gelatin, polyvinyl alcohol, and ethyl cellulose in addition to the same binder resin as that contained in the charge generation layer, and one or more of these materials are used. it can. Among these resins, polyamide resins are preferable, and alcohol-soluble nylon resins are particularly preferable.
Examples of alcohol-soluble nylon resins include copolymerized nylons obtained by copolymerizing 6-nylon, 6,6-nylon, 6,10-nylon, 11-nylon, 12-nylon, and the like; N-alkoxymethyl-modified nylon and N- Examples thereof include a resin obtained by chemically modifying nylon such as alkoxyethyl-modified nylon.

Examples of the solvent for dissolving or dispersing the resin material include water, alcohols such as methanol, ethanol and butanol, glymes such as methyl carbitol and butyl carbitol, and mixed solvents in which two or more of these solvents are mixed. Can be mentioned. Among these solvents, non-halogen organic solvents are preferably used in consideration of the global environment.
Other processes and conditions are in accordance with the formation of the charge generation layer.

The undercoat layer forming coating solution may contain metal oxide particles.
The metal oxide particles can easily adjust the volume resistance value of the undercoat layer, can further suppress the injection of charges into the laminated photosensitive layer, and can maintain the electrical characteristics of the photoreceptor in various environments.
Examples of the metal oxide particles include titanium oxide, aluminum oxide, aluminum hydroxide, and tin oxide.

When the total content of the resin material and metal oxide particles in the coating liquid for forming the undercoat layer is C and the content of the solvent is D, the weight ratio (C / D) of both is 1/99 to 40 / 60 is preferable, and 2/98 to 30/70 is particularly preferable.
Further, when the content of the resin material is E and the content of the metal oxide particles is F, the weight ratio (E / F) of both is preferably 1/99 to 90/10, and 5/95 to 70 /. 30 is particularly preferred.

Although the film thickness of an undercoat layer is not specifically limited, 0.01-20 micrometers is preferable and 0.05-10 micrometers is especially preferable.
If the thickness of the undercoat layer is less than 0.01 μm, the undercoat layer does not substantially function, and it is impossible to obtain a uniform surface property by covering defects of the conductive support. There is a possibility that charge injection into the photosensitive layer may not be prevented, and when the thickness of the undercoat layer exceeds 20 μm, it is difficult to form a uniform undercoat layer, and the sensitivity of the photoreceptor may be lowered. There is.
In addition, when the constituent material of an electroconductive support body is aluminum, the layer (alumite layer) containing an alumite can be formed and it can be set as an undercoat layer.

[Single-layer type photosensitive layer 204 ′]
The single-layer type photosensitive layer 204 ′ contains a charge generation material 202, a charge transport material 203, a diamine compound represented by the general formula (I), and a binder resin (binder) as main components.
The single-layer type photosensitive layer may contain an appropriate amount of the same additive as that contained in the charge generation layer, if necessary, within the range not impairing the effects of the present invention.

  Single layer type photoreceptors generally function as positively charged photoreceptors in general, and the amount of ozone and nitrogen oxides generated from the system is small compared to the case where they function as negatively charged photoreceptors. It can be said that the effect of imparting ozone resistance and oxidation gas resistance to the photoreceptor of the diamine compound represented by (I) is small. Therefore, it can be said that the laminated photoconductor has a larger effect of imparting oxidation resistance gas resistance of the diamine compound represented by the general formula (I).

The single-layer type photosensitive layer 204 ′ is prepared by dissolving and / or dispersing a charge generation material, a charge transport material, a diamine compound represented by the general formula (I) and other additives as required in a suitable organic solvent. A layer-type photosensitive layer forming coating solution is prepared, and this coating solution is applied to the surface of the conductive support 201 or the surface of the undercoat layer 207 formed on the conductive support 201, and then dried. Then, it can be formed by removing the organic solvent.
Other processes and conditions are in accordance with the formation of the charge generation layer and the charge transport layer.

  The thickness of the single-layer type photosensitive layer is not particularly limited, but is preferably 5 to 100 μm, particularly preferably 10 to 50 μm. If the film thickness of the single-layer type photosensitive layer is less than 5 μm, the charge holding ability on the surface of the photoreceptor may be lowered, and if the film thickness of the single-layer type photosensitive layer exceeds 100 μm, the productivity may be lowered. is there.

(Image forming device)
The image forming apparatus of the present invention includes a photosensitive member of the present invention, a charging unit that charges the photosensitive member, an exposure unit that exposes the charged photosensitive member, and an electrostatic latent image formed by the exposure. Developing means for forming a toner image, transfer means for transferring the developed toner image onto the recording material, fixing means for fixing the transferred toner image on the recording material to form an image, and a photoconductor A plurality of image forming units having at least cleaning means for removing and collecting the toner remaining on the recording medium; and a plurality of image forming units each having a different color toner on the recording medium. A color image is formed by superimposing sequentially.

Next, the image forming apparatus of the present invention will be specifically described with reference to FIG. 4, but the present invention is not limited thereby.
FIG. 4 is a schematic cross-sectional view of a color multifunction machine equipped with the photoreceptor of the present invention, showing an example of the image forming apparatus of the present invention.
As shown in FIG. 4, the image forming apparatus 1 includes a photosensitive drum 3 that carries a developer image (toner image) formed by a developer (toner) that matches each hue in accordance with color-separated image information. A plurality of process printing units 20 (20a, 20b, 20c, 20d) constituting an image forming unit having (3a, 3b, 3c, 3d) and toner images formed on the photosensitive drum 3 are temporarily stacked. An endless intermediate transfer belt (intermediate transfer member) 7 for transfer, a transfer portion (transfer mechanism) 11 for transferring a toner image from the intermediate transfer belt 7 to a recording sheet, and a toner image transferred to the recording sheet by heat fixing And a transfer belt cleaning unit (cleaning unit) 9 for removing toner remaining on the intermediate transfer belt 7 without being transferred from the intermediate transfer belt 7 onto the recording paper.

First, the overall configuration of the image forming apparatus 1 will be described.
As shown in FIG. 4, the image forming apparatus 1 is a so-called digital color multi-function peripheral that color-separates image information, forms an image for each hue, and outputs a color image. A multi-color image or a single-color image is formed on a recording sheet based on a print job from an information processing apparatus (not shown) such as a personal computer connected to the outside. It is. As the recording paper, resin sheets and metal sheets can be used as required in addition to paper.

  The image forming unit 108 forms a multicolor image using each color of yellow (Y), cyan (C), magenta (M), and black (BK) by an electrophotographic method. The unit 50, the process printing unit 20, the fixing unit 12, a transfer belt unit 8 as transfer means including the intermediate transfer belt 7, an intermediate transfer roller 6 (6 a, 6 b, 6 c, 6 d), and a transfer belt cleaning unit 9. ing.

The schematic configuration of the image forming unit 108 is that a fixing unit 12 is disposed on the upper end of one end of the casing 1 a of the image forming apparatus 1, and transferred from one end side to the other end side of the casing 1 a below the fixing unit 12. A belt unit 8 is disposed, a process printing unit 20 is disposed below the transfer belt unit 8, and an exposure unit 50 is disposed below the process printing unit 20.
A transfer belt cleaning unit 9 is provided on the other end side of the transfer belt unit 8. Further, a paper discharge tray 15 is provided above the image forming unit 108 adjacent to the fixing unit 12. A paper feeding unit 109 is configured below the image forming unit 108.

In the image forming apparatus 1, as the process printing unit 20, four process printing units 20a, 20b, 20c, and 20d corresponding to each color of black (BK), magenta (M), cyan (C), and yellow (Y) are provided. They are sequentially provided along the intermediate transfer belt 7. By the arrangement order of the respective colors, the toner images without color blur are superimposed on the intermediate transfer belt 7.
The process print unit 20d of the hue that is first transferred among the toner images transferred onto the intermediate transfer belt 7, that is, the process print unit 20d of the hue that is disposed farthest from the transfer unit 11 has a yellow hue. In this case, a yellow toner image is first formed on the intermediate transfer belt 7.

These process printing units 20a, 20b, 20c, and 20d are arranged in parallel in a substantially horizontal direction (left and right direction in the drawing) in the housing 1a, and the photosensitive drums 3a, 3b, which are image carriers for each color. 3c, 3d, chargers (charging means) 5a, 5b, 5c, 5d for charging the photosensitive drums 3a, 3b, 3c, 3d, developing devices (developing means) 2a, 2b, 2c, 2d, cleaner unit 4a, 4b, 4c, 4d, etc. are provided.
Here, the symbols a, b, c, and d attached to the components corresponding to the respective colors correspond to the respective colors of black (BK), magenta (M), cyan (C), and yellow (Y). However, in the following description, the constituent elements provided for each color are collectively shown in the photosensitive drum 3, except for the case where the constituent elements corresponding to a specific color are specified. The charger 5, the developing device 2, and the cleaner unit 4 are described.

  The photosensitive drum 3 is disposed so that a part of the outer peripheral surface thereof is in contact with the surface of the intermediate transfer belt 7, and the charger 5, the developing device 2, and the cleaner as an electric field generator along the outer peripheral surface of the drum. Units 4 are arranged close to each other.

The charger 5 is a roller-type charger and is disposed so as to contact the outer peripheral surface of the photosensitive drum 3 on the substantially opposite side to the position where the transfer belt unit 8 is disposed across the photosensitive drum 3. In this embodiment, a roller-type charger that generates less ozone and NOx is used as the charger 5, but a brush-type charger, a charger-type charger, or the like may be used instead of the roller-type charger.
In the image forming apparatus of the present invention, the charging unit of the image forming unit preferably includes a roller-shaped or brush-shaped charging member.

The exposure unit 50 applies laser light to each photosensitive drum 3 for each color based on the image data for printing, with respect to each photosensitive drum 3 whose drum surface is charged to a uniform potential by the charger 5. And a function of generating an electrostatic latent image on the surface of the photosensitive drum 3.
The exposure unit 50 mainly includes a laser scanning unit (LSU) 51 including a laser irradiation unit 51a, a polygon mirror 52, and reflection mirrors 53a, 53b, 53c, 53d, 54a, 54b that reflect laser light for each color, 54c and the like, and is an optical scanning device that emits laser light emitted from a laser irradiation unit 51a to a plurality of photosensitive drums 3a, 3b, 3c, and 3d, respectively.

  A laser scanning unit 51 is disposed at one end of the bottom of the housing 50a, and the polygon mirror 52, the fθ lens 55, the reflection mirrors 53a, 53b, 53c, and 53d are arranged from one end to the other end. Arranged in order.

The laser scanning unit 51 may use a writing head in which light emitting elements such as EL (Electro Luminescence) and LED (Light Emitting Diode) are arranged in an array instead of the laser irradiation unit 51a.
The fθ lens 55 includes two lenses. For example, the fθ lens 55 includes a cylinder lens 55a as a first lens and a toroidal lens 55b as a second lens.
On the upper surface of the housing 50a, an opening is formed that is long open along the direction along the axis of the photosensitive drum at a position facing the photosensitive drums 3a, 3b, 3c, and 3d. The condensing lenses 56a, 56b, 56c, and 56d that transmit the laser beams reflected by the reflecting mirrors 53d, 54a, 54b, and 54c and focus on the respective photosensitive drums 3a, 3b, 3c, and 3d are disposed. Has been.

The developing device 2 applies black (BK), magenta (M), cyan (C), and yellow (Y) to the electrostatic latent image formed by the exposure unit 50 described above on the outer peripheral surface of the photosensitive drum 3. A toner is supplied to make a visible image.
The developing device 2 stores toner of each color of black (BK), magenta (M), cyan (C), and yellow (Y) for each developing device 2, and rotates the photosensitive drum (in the drawing). (In the direction of arrow A) of FIG. Then, each color toner is supplied to the electrostatic latent image formed on the outer peripheral surface of the photosensitive drum 3 so as to be visualized.

The cleaner unit 4 removes and collects the toner remaining on the surface of the photosensitive drum 3 after the toner image on the surface of the photosensitive drum 3 developed by the developing device 2 is transferred to the intermediate transfer belt 7. The cleaner unit 4 is disposed downstream of the intermediate transfer belt 7 and upstream of the charger 5 along the photosensitive drum rotation direction.
In addition, the cleaner unit 4 includes a cleaning blade, and the cleaning blade is disposed in contact with the outer peripheral surface of the photosensitive drum 3 so as to scrape and collect residual toner on the photosensitive drum 3. Yes.

The transfer belt unit 8 is configured separately from the apparatus main body, and is detachably attached to the apparatus main body. The configuration mainly includes an intermediate transfer belt 7, a transfer belt drive roller 8-1, a transfer belt driven roller 8-2, a transfer belt tension mechanism 8-3, and intermediate transfer rollers 6a, 6b, 6c, and 6d. ing.
Then, the transfer belt unit 8 sequentially superimposes and transfers the toner images of the respective colors formed on the photosensitive drum 3 onto the intermediate transfer belt 7, thereby forming a color toner image (multicolor toner image) on the intermediate transfer belt 7. It has the function to form.
The intermediate transfer belt 7 is formed endless using chloroprene rubber as a material.
In addition, as a configuration of the intermediate transfer belt different from the present embodiment, a film having a thickness of about 75 μm to 120 μm using polyimide, polycarbonate, a thermoplastic elastomer alloy, or the like as a material may be formed endlessly. .

  Further, the intermediate transfer belt 7 has a transfer belt driving roller 8-1, a transfer belt driven roller 8-2, a transfer belt tension mechanism 8-3, an intermediate transfer so that the surface thereof is in contact with the outer peripheral surface of the photosensitive drum 3. It is stretched by a roller 6 and is configured to move in the sub-scanning direction (arrow B direction in the figure) by the driving force of the transfer belt driving roller 8-1.

The transfer belt drive roller 8-1 is disposed on one end side of the housing 1a, drives the intermediate transfer belt 7 to convey the intermediate transfer belt 7, and superimposes the intermediate transfer belt 7 and the recording paper. In this state, it is provided so as to convey the recording paper while being sandwiched between the transfer unit 11 (transfer roller 11a) and pressed.
The transfer belt driven roller 8-2 is disposed on the other end side of the housing 1a, and the intermediate transfer belt 7 is installed substantially horizontally from one end side to the other end side of the housing 1a together with the transfer belt driving roller 8-1. ing.

The intermediate transfer roller 6 is disposed in an inner space of the intermediate transfer belt 7 wound from the transfer belt driving roller 8-1 to the transfer belt driven roller 8-2, and presses the inner surface of the intermediate transfer belt 7, The outer surface of the intermediate transfer belt 7 is provided so as to contact a part of the outer peripheral surface of the photosensitive drum 3 to obtain a predetermined nip amount.
The intermediate transfer roller 6 includes a metal (for example, stainless steel) shaft having a diameter of 8 to 10 mm, and an outer peripheral surface of the metal shaft is covered with an elastic material having conductivity such as EPDM or urethane foam.

The intermediate transfer roller 6 configured in this manner is opposite to the high-voltage transfer bias, that is, the toner charging polarity (−), in order to transfer the toner image formed on the photosensitive drum 3 to the intermediate transfer belt 7. A high voltage of polarity (+) is applied, and the high voltage is uniformly applied to the intermediate transfer belt 7 by an elastic material.
In this embodiment, an intermediate transfer roller using a roller-shaped electrode is used as a configuration for performing intermediate transfer. However, as another method, a brush-shaped transfer electrode (transfer brush) is used as an intermediate transfer. The belt 7 may be in contact with the back side.

  On each of the above-described photosensitive drums 3, a visualized toner image (electrostatic image) corresponding to each hue is laminated by the intermediate transfer belt 7 and becomes image information input to the apparatus. The image information stacked in this way is transferred to a recording sheet by a transfer unit 11 disposed at a contact position of the intermediate transfer belt 7.

  The transfer unit 11 constitutes transfer means for transferring the developer image transferred to the intermediate transfer belt 7 to a recording sheet, and includes a transfer roller 11a. The transfer roller 11a is connected to the transfer belt drive roller 8-1. It is arranged so as to be substantially horizontal and parallel to the intermediate transfer belt 7 wound around the transfer belt driving roller 8-1, so as to come into pressure contact with the intermediate transfer belt 7 at a predetermined nip via the conveyance belt 11b.

The transfer roller 11a applies a voltage for transferring the multicolor toner image formed on the intermediate transfer belt 7 onto the recording paper, that is, a high voltage having a polarity (+) opposite to the toner charging polarity (-). It is configured to be.
Further, one of the transfer roller 11a and the transfer belt drive roller 8-1 is made of a hard material (metal or the like), and the other is a soft material (elastic rubber roller, foaming resin roller or the like) on the surface of the core metal. Is constituted by an elastic roller covered with As a result, a nip having a predetermined width is constantly obtained.

A registration roller 14 is provided below the transfer belt drive roller 8-1 and the transfer unit 11. The registration roller 14 is configured to convey the leading end of the recording paper supplied from the paper feeding unit 109 and the leading end of the toner image on the intermediate transfer belt 7 to the transfer unit 11 side.
Further, as described above, the toner adhering to the intermediate transfer belt 7 due to contact with the photosensitive drum 3 or the toner remaining on the recording paper without being transferred onto the recording paper by the intermediate transfer roller 6 is used in the next step. Since it causes toner color mixing, it is set so as to be removed and collected by the transfer belt cleaning unit 9.

  The transfer belt cleaning unit 9 is provided in the vicinity of the transfer belt driven roller 8-2, and is disposed so as to contact (or slide) the intermediate transfer belt 7, and the intermediate transfer belt by the cleaning blade 9a. 7 and a box-shaped toner collecting portion 9b for temporarily storing the toner (waste toner) scraped off from the residual toner on the intermediate transfer belt 7. The residual toner on the intermediate transfer belt 7 is scraped and collected. The collected waste toner is conveyed to a waste toner collection container 9c.

  Further, the transfer belt cleaning unit 9 is disposed in the vicinity of the process printing unit 20a on the upstream side in the moving direction of the intermediate transfer belt 7 from the process printing unit 20a. The portion of the intermediate transfer belt 7 where the cleaning blade 9a contacts the outer surface is supported by the transfer belt driven roller 8-2 on the inner surface.

As shown in FIG. 4, the fixing unit 12 includes a pair of fixing rollers 12 a composed of a heating roller 31 and a pressure roller 32, and a conveying roller 25-5 above the fixing roller 12 a, and records paper. It is carried in from below the fixing roller 12a and carried out upward.
Further, above the fixing unit 12, a paper discharge roller 25-6 is provided adjacent to the transport roller 25-5, and the recording paper transported from the transport roller 25-5 is discharged by the paper discharge roller 25-6. The recording paper is discharged onto the paper tray 15.

The fixing of the toner image by the fixing unit 12 is controlled by controlling heating means (not shown) such as a heater lamp provided inside or close to the heating roller 31 based on a detection value of a temperature detector (not shown). The heating roller 31 is kept at a predetermined temperature (fixing temperature), and the recording paper on which the toner image is transferred is heated and pressed while being rotated and conveyed while being sandwiched between the heating roller 31 and the pressure roller 32. The toner image is thermally fixed.
The paper feeding unit 109 includes a plurality of paper feeding trays 10 for storing recording papers used for image formation, and supplies the recording papers one by one from the paper feeding tray 10 to the image forming unit 108. .

The paper feed tray 10 is provided below the image forming unit 108 and the exposure unit 50 in the housing 1a and accommodates a large amount of recording paper having a size defined by the specifications of the apparatus or a size predetermined by the user. It is possible.
Pickup rollers 16 are respectively provided on one end portion (left end portion in the figure) of the paper feed tray 10, and the surface of one end portion of the recording paper at the top of the recording paper set in the paper feed tray 10 The rollers are brought into contact with each other and reliably fed out one by one by the frictional resistance of the rollers.

A paper discharge tray 15 is provided at the top of the image forming apparatus 1 so that printed recording paper is discharged face down and stacked.
In addition, the sheet feeding unit 109 has a substantially vertical sheet conveyance path S for conveying the recording sheet in the sheet feeding tray 10 to the sheet discharge tray 15 provided above via the transfer unit 11 and the fixing unit 12. Is configured.
Further, in the vicinity of the paper conveyance path S from the paper feed tray 10 to the paper discharge tray 15, a pickup roller 16, a registration roller 14, a transfer unit 11, a fixing unit 12, and a conveyance roller 25 (25-) for conveying recording paper. 1-25-8) are arranged.

  The registration roller 14 temporarily stops the recording sheet conveyed by the sheet conveyance path S at a predetermined position and measures the next conveyance timing. The recording paper has a function of conveying the recording paper to the transfer section 11 at a timing at which the leading edge of the toner image on the intermediate transfer belt 7 is synchronized with the leading edge of the recording paper.

The recording paper transported from the paper feed tray 10 is transported to the registration rollers 14 by the transport rollers 25-1 to 25-4 in the transport path, and is temporarily stopped. The toner image on the transfer belt 7 is conveyed to the transfer unit 11 at a timing for aligning the leading end of the toner image.
The transferred recording sheet is transferred with the toner image on the intermediate transfer belt 7 by the transfer unit 11 and further transferred to the fixing unit 12 where the unfixed toner on the recording sheet is melted by heat and fused to the recording sheet. To do. After passing through the fixing unit 12, it is naturally cooled and fixed on the recording paper. Then, the recording paper is discharged onto the paper discharge tray 15 from the paper discharge roller 25-6 via the transport roller 25-5.
The recording paper after the fixing of the multicolor toner image is conveyed to the reverse paper discharge path of the paper conveyance path S by the conveyance rollers 25-5 and 25-6, and is reversed (the multicolor toner image is placed on the lower side). Toward the paper discharge tray 15.

A control board 40 is disposed below the paper discharge tray 15.
The control board 40 provides a microcomputer for controlling the operation of each part of the image forming apparatus 1, a ROM for storing a control program executed by the microcomputer, a work area for processing of the microcomputer, and a storage area for image data. RAM to be used.

  The microcomputer functions as a control unit by executing a control program. The functions of the control unit realize the above-described image formation, toner image transfer, recording paper conveyance, fixing unit temperature control, and the like.

  The control board 40 has an input circuit and an output circuit. The input circuit is configured such that signals from sensors arranged in the respective units in the image forming apparatus 1 are input, and processing by the microcomputer is executed using the input signals. The output circuit is a circuit that outputs a signal for driving a load disposed in each part.

The image forming unit of the image forming apparatus of the present invention preferably includes an intermediate transfer member. Thereby, a color image forming apparatus capable of high-speed printing can be provided.
The charging means in the image forming unit of the image forming apparatus of the present invention is preferably a contact charging method. As a result, the ozone amount and the NOx amount can be suppressed to be smaller than those of the conventional corona charging method, and a high-speed and highly durable image forming apparatus can be provided.

  The present invention will be specifically described below with reference to production examples, examples and comparative examples, but the present invention is not limited to these production examples and examples.

(Production Example 1)
Dibenzylamine is used as the amine compound represented by general formula (IV) and general formula (V), and 4,4′-bis (chloromethyl) phenyl is used as the dihalogen compound represented by general formula (IX). According to Exemplified Compound No. 2 was produced.

In 50 ml of anhydrous 1,4-dioxane, 6.06 g (1.0 equivalent) of 4,4′-bis (chloromethyl) phenyl and 10.0 g (2.1 equivalent) of dibenzylamine were added, and the temperature was below freezing in an ice bath. Cooled to. To this solution, 6.86 g (2.2 equivalents) of N, N-diisopropylethylamine was gradually added. Thereafter, the ice bath was removed, the mixture was gradually heated using an oil bath to raise the reaction temperature to 100 to 110 ° C., and stirred for 4 hours while heating to maintain 100 to 110 ° C. After completion of the reaction, the reaction solution is allowed to cool, and the resulting precipitate is collected by filtration, sufficiently washed with water, and recrystallized with a mixed solvent of ethanol and ethyl acetate (ethanol: ethyl acetate = 8: 2 to 7: 3). To obtain 11.9 g of a white powdery compound.
The chemical structure, molecular weight and elemental analysis of the obtained compound were measured by NMR, LC-MS, elemental analysis and FT-IR to confirm that the desired compound was obtained.

(Production Examples 2 to 11)
In Production Example 1, amine compounds represented by the general formulas (IV) and (V) and dihalogen compounds represented by the general formula (VI) were used in the same manner as in Production Example 1, using each raw material compound shown in Table 2. Exemplified Compound No. 1, 4, 8, 14, 22, 29, 38, 50, 53 and 57 were produced, respectively. In Table 2, Exemplified Compound No. 2 raw material compounds are also shown.

  Moreover, the element analysis value of each exemplary compound obtained by said manufacture examples 1-11, the calculated value of molecular weight, and the measured value [M + H] by LC-MS are shown in the following tables.

Example 1
3 parts by weight of titanium oxide (trade name: Taibake TTO55A, manufactured by Ishihara Sangyo Co., Ltd.) and 3 parts by weight of a copolymer nylon resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.), 65 parts by weight of methyl alcohol and 1,3- were added to a mixed solvent of dioxolane 35 parts by weight, was manufactured by adjusting the undercoat layer coating liquid was dispersed for 8 hours by a paint shaker. This coating solution is filled in a coating tank, and an aluminum drum-shaped support body having a diameter of 30 mm and a total length of 350 mm is immersed as a conductive support, and then pulled up and dried naturally to form an undercoat layer having a thickness of 1 μm on the conductive support. Formed.

  Next, a perylene pigment represented by the following structural formula (A) as a charge generating substance (for example, prepared by a known method described in Bulletin of the Chemical Society of Japan, vol. 25 (1952), p411-413) 2 weight Parts and polyvinyl butyral resin (trade name: ESREC BMS, manufactured by Sekisui Chemical Co., Ltd.) in addition to 97 parts by weight of tetrahydrofuran and dispersed in a ball mill for 72 hours to prepare a charge generation layer coating solution. This coating solution was applied onto the previously provided undercoat layer by the same dip coating method as that for the undercoat layer, and then naturally dried to form a charge generation layer having a thickness of 0.5 μm.

Next, 100 parts by weight of a triarylamine compound represented by the following structural formula (B) as a charge transporting material (manufactured by Nippon Distilling Industry Co., Ltd.), polycarbonate resin (trade name: TS2040, manufactured by Teijin Chemicals Ltd.) 160 as a binder resin 3 parts by weight of the diamine compound (Exemplary Compound No. 2) obtained in Production Example 1 as parts by weight and additives were dissolved in 980 parts by weight of tetrahydrofuran to prepare a charge transport layer coating solution. This coating solution is applied onto the charge generation layer previously provided by the same dip coating method as that of the undercoat layer, and the resulting coating film is dried at 130 ° C. for 1 hour to form a charge transport layer having a thickness of 22 μm. did.
The photoreceptor shown in FIG. 2 was produced by the above process.
In addition, a photoreceptor having a charge transport layer having a film thickness of 15 μm was similarly prepared for evaluation of ozone gas resistance, which will be described later.

(Examples 2 to 4)
Instead of the diamine compound (Exemplary Compound No. 2) as an additive for the charge transport layer coating solution, Exemplified Compound No. A photoconductor shown in FIG. 2 was produced in the same manner as in Example 1 except that 1, 4, and 8 were used.

(Example 5)
A photoconductor shown in FIG. 2 was produced in the same manner as in Example 1 except that 0.1 part by weight of a diamine compound (Exemplary Compound No. 2) as an additive for the charge transport layer coating solution was used.

(Example 6)
A photoconductor shown in FIG. 2 was produced in the same manner as in Example 1 except that 20 parts by weight of a diamine compound (Exemplary Compound No. 2) as an additive for the charge transport layer coating solution was used.

(Example 7)
A photoconductor shown in FIG. 2 was produced in the same manner as in Example 1 except that 0.05 part by weight of a diamine compound (Exemplary Compound No. 2) as an additive for the charge transport layer coating solution was used.

(Example 8)
A photoconductor shown in FIG. 2 was prepared in the same manner as in Example 1 except that 25 parts by weight of a diamine compound (Exemplary Compound No. 2) as an additive for the charge transport layer coating solution was used.

Example 9
A photoconductor shown in FIG. 2 is produced in the same manner as in Example 1 except that 120 parts by weight of a polycarbonate resin (trade name: TS2040, manufactured by Teijin Kasei Co., Ltd.) is used as the binder resin of the coating solution for the charge transport layer. did.

(Example 10)
The photoreceptor shown in FIG. 2 is produced in the same manner as in Example 1 except that 300 parts by weight of polycarbonate resin (trade name: TS2040, manufactured by Teijin Kasei Co., Ltd.) is used as the binder resin of the charge transport layer coating solution. did.

(Example 11)
The photoreceptor shown in FIG. 2 is produced in the same manner as in Example 1 except that 100 parts by weight of polycarbonate resin (trade name: TS2040, manufactured by Teijin Kasei Co., Ltd.) is used as the binder resin of the charge transport layer coating solution. did.

(Example 12)
The photoconductor shown in FIG. 2 is produced in the same manner as in Example 1 except that 320 parts by weight of polycarbonate resin (trade name: TS2040, manufactured by Teijin Chemicals Ltd.) is used as the binder resin of the coating solution for the charge transport layer. did.

(Example 13)
A photoconductor shown in FIG. 1 was produced in the same manner as in Example 1 except that no undercoat layer was formed.

(Example 14)
2 parts by weight of the perylene pigment represented by the structural formula (A) as a charge generating material is mixed with 100 parts by weight of tetrahydrofuran, dispersed for 12 hours in a paint shaker, and then used as the charge transporting material in the structural formula (B). 100 parts by weight of the triarylamine compound shown, 160 parts by weight of a polycarbonate resin (trade name: TS2040, manufactured by Teijin Chemicals Ltd.) as a binder resin, and the diamine compound (Exemplary Compound No. 2) obtained in Production Example 1 as an additive 3 parts by weight was dissolved in 880 parts by weight of tetrahydrofuran and stirred to prepare a photosensitive layer coating solution. This coating solution was applied onto an aluminum drum-shaped support having a diameter of 30 mm and a total length of 350 mm as a conductive support by the same dip coating method as that of the undercoat layer of Example 1, and the resulting coating film was applied to 130. The film was dried at 0 ° C. for 1 hour to form a single-layer type photosensitive layer having a thickness of 22 μm.
The photoconductor shown in FIG. 3 was produced by the above process.
In addition, a photoreceptor having a single-layer type photosensitive layer having a film thickness of 15 μm was similarly prepared for evaluation of ozone gas resistance described later.

(Comparative Example 1)
A photoconductor shown in FIG. 2 was produced in the same manner as in Example 1 except that no additive was used in the charge transport layer coating solution.

(Comparative Example 2)
Instead of the diamine compound as an additive for the charge transport layer coating solution, a known compound represented by the following structural formula (C) (hindered phenol, trade name: K-NOX BHT, manufactured by Kyodo Yakuhin Co., Ltd.) is used. Except for this, a photoconductor shown in FIG. 2 was produced in the same manner as in Example 1.

(Comparative Example 3)
Example 1 except that a known antioxidant (hindered amine, manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (D) is used instead of the diamine compound as an additive for the charge transport layer coating solution. Similarly, the photoreceptor shown in FIG. 2 was produced.

(Comparative Example 4)
Similar to Example 1 except that a known antioxidant (hindered amine, manufactured by Nagase Sangyo Co., Ltd.) represented by the following structural formula (E) is used in place of the diamine compound as an additive for the charge transport layer coating solution. Thus, the photoreceptor shown in FIG. 2 was produced.

(Evaluation 1)
For each of the produced photoreceptors of Examples 1 to 14 and Comparative Examples 1 to 4, the sensitivity (electrical characteristics), printing durability, ozone gas resistance, image and color difference of the photoreceptor are evaluated as follows. A comprehensive evaluation was performed.

A color tandem digital multifunction machine (model: ARC-260, manufactured by Sharp Corporation) modified for testing so that the developing device and the surface potential measuring device can be replaced with a semiconductor laser (oscillation wavelength 489.9 nm) as an exposure light source. , Manufactured by Sony Corporation) and mounted with a photoconductor.
Next, using this multi-function machine, 100,000 sheets of character test charts were formed by the following method to evaluate sensitivity, printing durability, and images (monochrome printing was used during sample image output and image formation). ).

[Sensitivity (Electrical characteristics)]
The developing device was removed from the multifunction peripheral, and a surface electrometer (model: model 344, manufactured by Trek Japan) was attached instead. The surface potential of the photoconductor when this compound machine is not exposed to laser light in a normal temperature / normal humidity (N / N) environment at a temperature of 25 ° C. and a relative humidity of 50%. Was adjusted to -600V. In this state, the photosensitive member was exposed with laser light (1.0 μJ / cm ² ), and the initial surface potential of the photosensitive member was set to the exposure potential VL1 (−V). Subsequently, the surface potential after the printing durability test was measured as the exposure potential VL2 (−V) by printing a character test chart (ISO19752) on 100,000 sheets of recording paper.
The sensitivity was evaluated from the obtained VL according to the following criteria.
The smaller the difference in exposure potential difference ΔVL before and after the printing durability test, the better the repeatability. In addition, the smaller the absolute value, the higher the sensitivity of the photoreceptor.

<Criteria>
A: | ΔVL | <50 (V)
○: 50 (V) ≦ | VL | <80 (V)
×: 80 (V) ≦ | VL |

[Press life]
The pressure of the cleaning blade of the cleaning device provided in the digital multi-function peripheral was adjusted to 21 gf / cm (2.06 × 10 ⁻¹ N / cm: initial linear pressure). A printing test was performed by printing a character test chart (ISO19752) on 100,000 sheets of recording paper in an N / N environment.
The thickness of the photosensitive layer at the start of the printing durability test and after the formation of 100,000 sheets of images was measured using a film thickness measuring device (model: F-20-EXR, manufactured by Filmetrics).
From the difference between the film thickness at the start of the printing test and the film thickness after the 100,000-sheet image is formed, the amount of abrasion per 100,000 revolutions of the photosensitive drum is obtained, and the printing durability is determined from the obtained amount of abrasion using the following criteria. evaluated.
In addition, it means that printing durability is so bad that there is much scraping amount.

<Criteria>
A: Cutting amount d <3.5 μm / 100 k rotation ○: 3.5 μm / 100 k rotation ≦ Scraping amount d <5.5 μm / 100 k rotation ×: 5.5 μm / 100 k rotation ≦ Scraping amount d

[Ozone gas resistance]
A photoconductor prepared for evaluation of ozone gas resistance was used (the film thicknesses of the charge transport layer of the multilayer photoconductor and the single-layer photolayer of the single-layer photoconductor are each 15 μm).
Mount the photoconductor on the digital multi-function peripheral and measure the surface potential V ₁ (V) of the photoconductor immediately after charging and the surface potential V ₂ (V) of the photoconductor 3 seconds after charging in an N / N environment. did.
The measured values were substituted into the following formula to calculate the charge retention rate DD (percent), which was used as initial charge retention rate DD _0.

Next, the photoconductor was exposed to ozone for 20 hours in a sealed container adjusted to an ozone concentration of about 7.5 ppm using an ozone generation / control device (trade name: OES-10A, manufactured by Dilec Co., Ltd.). The ozone concentration was confirmed with an ozone densitometer (model: MODEL1200, manufactured by Direc Co., Ltd.).
After ozone exposure, after the photosensitive member was left for 2 hours under N / N environment, in the same manner as before ozone exposure determined charge retention rate DD (percent), which was used as a charge retention rate DD ₀₂ after ozone exposure.

A value obtained by subtracting the charge retention ratio DD ₀₂ after ozone exposure from the charge retention ratio before exposure to ozone (initial charge retention ratio DD ₀ ) is obtained as a charge retention ratio change amount ΔDD (= DD ₀ -DD ₀₂ ), As an evaluation index of sex, it was evaluated according to the following criteria.

<Criteria>
A: ΔDD <3.5
○: 3.5 ≦ ΔDD <5.0
×: 5.0 ≦ ΔDD

[image]
(1) Image determination (dot / character reproducibility <sharpness>)
1 dot 1 space image and 5 points equivalent to 1200 dpi before starting printing test in a normal temperature / low humidity (N / L) environment with a temperature of 25 ° C and a relative humidity of 20%. The character image of was output. From these images, the following criteria were evaluated.
A: Visually clear image with no abnormality on the image.
○: A level in which some dots and characters are disturbed on the image by visual inspection, but there is no problem in actual use.
X: An image that is visually blurred due to disturbance of dots and characters on the image.

(2) Image determination (density unevenness)
The level of image quality degradation after the printing durability test was evaluated according to the following criteria by outputting a halftone image.
A: There is no density unevenness in the image visually. Good picture.
○: Density unevenness in the image visually. There is no problem in actual use.
X: Density unevenness in image visually. A level that causes problems in actual use.

(3) Image determination (image blur)
The level of image quality degradation after the printing durability test was evaluated according to the following criteria by outputting a 1-dot 1-space image equivalent to 1200 dpi and a 5-point character image.
(Double-circle): There is no image blur on an image visually. Good picture.
◯: Partial image blur occurred on the image by visual inspection, but at a level where there is no problem in actual use.
X: One or more image blurs occur on several or part of the image visually.

[Color difference of photoconductor]
The presence or absence of color change in the photoreceptor before and after the ozone exposure test was visually confirmed.

[Comprehensive evaluation / (Electrical characteristics, printing durability, image evaluation)]
Based on the determination results of the above seven items, evaluation was performed according to the following criteria.
◎: All 7 items ○
○: ◎ or ○ for all 7 items
×: At least one or more ×
The above evaluation results are shown in Table 4.
In the table, CTM / CTB indicates the weight ratio of the charge transport material / binder resin.

The following can be understood from comparison with Examples 1 to 14 and Comparative Examples 1 to 4.
(1) General formula (I) as an additive in a single layer type photosensitive layer or a charge transport layer of a multilayer type photosensitive layer
The photoconductors of Examples 1 to 14 containing the diamine compound represented by the formulas are initial sensitivity, stability of electrical characteristics in repetition, printing durability due to repeated fatigue, oxidizing gas stability after exposure to ozone, and image evaluation. Good results were obtained. On the other hand, the photoreceptors of Comparative Examples 1 to 4 containing no additive or containing other additives have a potential increase after repetition, an increase in film loss, a significant decrease in charge retention after exposure to ozone, and Any defect such as an image defect was observed. At the same time, there was a difference in color between the photoconductors with a tendency to deteriorate before and after exposure.

  In the photoreceptors of Comparative Examples 1 to 4, the charge transport material and the charge generation material are decomposed and deteriorated, and the transmittance is lowered due to the coloring of the oxidized product accompanying the reaction of the antioxidant, thereby significantly deteriorating the electrical stability. It is considered that the printing durability of the surface layer of the photoreceptor affected by the acid gas deteriorated, the sharpness caused by the oxidation product decreased, image blurring and image unevenness occurred.

(2) The photoreceptors of Examples 1, 5, and 6 in which the content of the diamine compound represented by the general formula (I) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the charge transport material are electrically stable. , Printing durability, gas stability, and image evaluation are all excellent. On the other hand, the photoreceptor of Example 7 having a diamine compound content of less than 0.1 parts by weight can withstand practical use, but there is a slight increase in sensitivity after the printing durability test and blurring of character images. Has fallen. Further, the photoreceptor of Example 8 having a diamine compound content of more than 20% can withstand practical use, but a significant increase in sensitivity was observed.
From these results, it is understood that the content of the diamine compound is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the charge transport material.

(3) From the results of Examples 1 and 9 to 12, a photoreceptor having a binder resin content of 120 to 300 parts by weight with respect to 100 parts by weight of the charge transport material is particularly stable and mechanically durable in repeated use. It turns out that it is excellent in property. The photoconductor of Example 11, which is smaller than the above range, can withstand practical use, but there are some image defects after printing (improper character reproducibility) and a decrease in charge retention after exposure. It was. The photoreceptor of Example 12, which is larger than the above range, can withstand practical use, but some image defects (image unevenness) after printing were observed.

(4) From the results of Examples 1 and 13, it can be seen that it is preferable to provide an undercoat layer. That is, the photoconductor of Example 13 having no undercoat layer is inferior in sensitivity characteristics and weak in ozone resistance as compared with the photoconductor of Example 1 having an undercoat layer.

(Evaluation 2)
The photoconductor was evaluated in the same manner as in Evaluation 1 except that the printing / evaluation image was changed from monochrome printing to four-color printing.

In the photoconductor of the present invention containing the diamine compound represented by the general formula (I), sharpness improvement by a short wavelength laser is more noticeable in image formation by color four-color printing than monochrome printing.

  From the above, by including the diamine compound used in the present invention, even in the case of using a short wavelength laser, it is excellent in mechanical and electrical durability for initial and repeated use, and It can be seen that it is possible to provide an electrophotographic photosensitive member that does not generate an abnormal image such as image blur and can stably output a high-quality image over a long period of time.

FIG. 3 is a schematic cross-sectional view illustrating a configuration of a main part of the photoconductor of the present invention. FIG. 3 is a schematic cross-sectional view illustrating a configuration of a main part of the photoconductor of the present invention. FIG. 3 is a schematic cross-sectional view illustrating a configuration of a main part of the photoconductor of the present invention. FIG. 2 is a schematic cross-sectional view of a color complex machine equipped with the photoreceptor of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Image forming apparatus 1a, 50a Case 2, 2a, 2b, 2c, 2d Developing device (developing means)
3, 3a, 3b, 3c, 3d photoconductor (photoconductor drum)
4, 4a, 4b, 4c, 4d Cleaner unit 5, 5a, 5b, 5c, 5d Charger (charging means)
6, 6a, 6b, 6c, 6d Intermediate transfer roller 7 Intermediate transfer belt (intermediate transfer member)
8 Transfer belt unit (intermediate transfer unit)
8-1 Transfer belt drive roller 8-2 Transfer belt driven roller 8-3 Transfer belt tension mechanism 9 Transfer belt cleaning unit (cleaning unit)
9a Cleaning blade 9b Toner recovery unit 10 Paper feed tray

11 Transfer section (transfer mechanism)
11a Transfer roller 12 Fixing unit 14 Registration roller 15 Paper discharge tray 16 Pickup roller 20, 20a, 20b, 20c, 20d Process printing unit (image forming unit)
Conveyance roller 25 (25-1 to 25-8)
31 Heating roller 32 Pressure roller 40 Control board

50 Exposure unit 51 Laser scanning unit (LSU)
51a Laser irradiation unit 52 Polygon mirror 53a, 53b, 53c, 53d, 54a, 54b, 54c Reflective mirror 55a Cylinder lens 55b Toroidal lens 56a, 56b, 56c, 56d Condensing lens 108 Image forming unit 55 fθ lens 109 Paper feeding unit

DESCRIPTION OF SYMBOLS 101,102,103 Photoconductor 201 Conductive support body 202 Charge generation material 203 Charge transport material 204 Multilayer type photosensitive layer 204 'Single layer type photosensitive layer 205 Charge generation layer 206 Charge transfer layer 207 Undercoat layer (intermediate layer)

Claims (6)

On the conductive support, a single-layer type photosensitive layer containing at least a charge generation material and a charge transport material, or a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material in this order. A laminated type photosensitive layer is laminated,
The charge transport layer of the single-layer type photosensitive layer or the multilayer type photosensitive layer has the sub-formula (III):
[Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are a phenyl group or a 4-methoxyphenyl group, or Ar ¹ and Ar ⁴ are a 2,4-xylyl group and Ar ² and Ar ³ are Ri cyclohexyl der, Ar ⁵ is Ru 1,4-naphthylene group der]
And is used in an image forming apparatus provided with an exposure means for forming an electrostatic latent image by exposure using a semiconductor laser or a light emitting diode having an oscillation wavelength of 350 to 500 nm as an exposure light source. An electrophotographic photoreceptor.   The electrophotographic photosensitive member according to claim 1, wherein the content of the diamine compound is 0.1 to 20 parts by weight with respect to 100 parts by weight of the charge transport material.   The charge transport layer of the single layer type photosensitive layer or the multilayer type photosensitive layer contains a binder resin, and the content of the binder resin is 120 to 300 parts by weight with respect to 100 parts by weight of the charge transport material. 3. The electrophotographic photosensitive member according to 1 or 2.   The electrophotographic photosensitive member according to any one of claims 1 to 3, further comprising an undercoat layer between the conductive support and the single-layer photosensitive layer or the laminated photosensitive layer.   5. The electrophotographic photosensitive member according to claim 1, charging means for charging the electrophotographic photosensitive member, and an oscillation wavelength of 350 to 500 nm as an exposure light source for the charged electrophotographic photosensitive member. An exposure means for forming an electrostatic latent image by performing exposure using a semiconductor laser or a light emitting diode, a developing means for developing the electrostatic latent image formed by exposure to form a toner image, and the developed Transfer means for transferring the toner image onto the recording material, fixing means for fixing the transferred toner image on the recording material to form an image, and cleaning for removing and collecting the toner remaining on the electrophotographic photosensitive member An image forming apparatus comprising at least means.   A plurality of image forming apparatuses according to claim 5 are provided as a unit, and a color image is formed by sequentially superimposing different color toner images on a recording medium using a different color toner for each of the plurality of image forming apparatuses. Forming an image forming apparatus.