JPH0895264A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE: To ensure high sensitivity, superior wear and printing resistances and high lubricity and to suppress the deterioration of potential stability, the increase of residual potential and the lowering of photosensitivity by incorporating grafted polycarbonate resin having a specified organosiloxane structure. CONSTITUTION: Grafted polycarbonate resin having an organosiloxane structure represented by the formula is incorporated into a layer of an electrophotographic photoreceptor. In the formula, each of R1 and R2 is H, halogen, optionally substd. 1-6C alkyl or optionally substd. aryl, R3 is 1-6C alkylene or 1-6C alkylidene, each of R4 -R7 is optionally substd. 1-12C alkyl, optionally substd. cycloalkane or optionally substd. phenyl, each of (a) and (b) is an integer of 1-4 and (m) is an integer of 1-500. The grafted polycarbonate resin is preferably incorporated into the outermost layer farthest from the substrate among the constituent layers of the photoreceptor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor in the field of electrophotography, and more particularly to an organic electrophotographic photoconductor used by being incorporated in a copying machine or a printer.

[0002]

Description of the Related Art A copying machine using the Carlson method, which is the most representative of conventional electrophotographic methods, will be described. After uniformly charging the photosensitive member, the charge is erased in an imagewise manner by exposure, and the electrostatic charge latent image is erased. Form an image. This is developed with toner to be visualized, and then the toner is transferred to a transfer body such as paper and then fixed. On the other hand, the photoconductor is subjected to surface cleaning treatment such as removal of remaining adhered toner and static elimination, and is repeatedly used for a long period of time. Therefore, as an electrophotographic photosensitive member, of course, it has good electrification characteristics and sensitivity, and also has low dark decay. In addition to electrophotographic characteristics, it also has printing durability after repeated use, abrasion resistance, and scratches on the surface. It is required to have good physical properties such as difficulty, resistance to ozone generated by corona discharge, and durability to ultraviolet rays received at the time of exposure, and these points are regarded as problems in practical use.

So-called inorganic photoconductors having an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium as the main component of the photoconductive layer have been widely used as electrophotographic photoconductors. However, many of these inorganic photoconductors are harmful and pose a problem in terms of environmental measures. Therefore, in recent years, the development of organic photoconductors using organic substances which are non-polluting has been actively pursued and has been widely put into practical use. Above all, so-called function-separated type photoreceptors in which different substances having a charge generating function and a charge transporting function are shared and a compound having desired properties can be selected from a wide range have been actively developed. However, such an organic photoconductor is generally inferior in mechanical strength to an inorganic photoconductor, and there is a problem such as rubbing and abrasion due to a mechanical external force of a cleaning blade, a developing brush or the like.

For example, in a conventional photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a support, the charge transport layer is formed by binding a low molecular weight charge transport material with an inert polymer resin binder. Since the charge transport layer is formed, it is generally soft, and it is not always possible to achieve both mechanical properties and electrophotographic properties. With a highly sensitive composition or a certain kind of resin binder, when the photoreceptor is repeatedly used, the surface of the photoreceptor is scratched or scratched by rubbing of a cleaning blade, etc. The resin binder of 1) was not satisfactory in electrophotographic characteristics such as low sensitivity or increase of residual charge. These are obstacles to speeding up or downsizing of the Carlson process, which has been strongly oriented in recent years.

With respect to these problems, a silicone-containing resin is used in the charge transport layer as a reducing agent for reducing the friction coefficient of the surface of the photoconductor, reducing the surface energy, and a wear reducing agent (JP-A-61-2).
No. 19049, No. 62-205357), a fluorine-containing resin (JP-A-50-23231, No. 61-11636).
No. 2, No. 61-204633, No. 61-270768
No.) etc. have been proposed. However, electrophotographic characteristics such as low sensitivity and increase in residual potential due to repeated use,
Mechanical durability such as abrasion during repeated use, deterioration of image quality due to scratches, and deterioration of sensitivity due to film abrasion is still insufficient, and no resin satisfying these requirements has been found. Further, it has been proposed to solve the problems by further providing a protective layer with various compositions and materials on the charge transport layer, but the sensitivity is lowered and the residual charge is increased. Further, a method for solving the problems by increasing the molecular weight of the binder resin is disclosed in JP-A-60-16.
8153 and JP-A-1-206348, the viscosity of the coating solution exponentially increases as the molecular weight increases. Therefore, in dip coating, which is a general coating method for the charge transport layer, it is necessary to slowly pull up the coating in order to coat the charge transport layer to an appropriate thickness, resulting in a decrease in productivity.

Further, for example, a copolycarbonate resin using a diphenol compound having an organosiloxane structure as a monomer has been proposed as a means for solving these problems (JP-A-5-72753 and JP-A-5-8).
8398, JP-A-6-136108). However,
Although these linear copolymers are effective in reversing the cleaning blade, they still have insufficient mechanical properties and the abrasion of the electrophotographic photosensitive member surface is sufficiently improved by friction with the cleaning blade and the transferred member. It has not been.

[0007]

DISCLOSURE OF THE INVENTION The present invention has high sensitivity, excellent wear resistance and printing durability, high lubricity, and reduced potential stability due to repeated use, increased residual potential and increased photosensitivity. An object is to provide an electrophotographic photosensitive member with less deterioration.

[0008]

DISCLOSURE OF THE INVENTION As a result of studies by the present inventors, the photo-fatigue such as decrease in potential stability, increase in residual potential, and decrease in sensitivity of a photoreceptor caused by repeated use, ozone resistance, and degree of wear are regarded as charge. It was found that in addition to the wear resistance of the transport layer, it depends largely on the slip property of the surface.

The present inventor has found that the above-mentioned objects are represented by the general formula (1):
The present invention has been completed by discovering that it can be achieved by an electrophotographic photoreceptor containing a grafted hypolycarbonate resin having an organosiloxane structure represented by (hereinafter also referred to as a resin of the present invention).

Furthermore, the present inventor has also found that the embodiment in which the resin of the present invention is contained in the outermost layer farthest from the support in the constituent layers of the electrophotographic photoreceptor is preferable.

Further, the present inventor further added a charge transport layer to
The present inventors have completed the present invention by finding that a multi-layer electrophotographic photoconductor having more than one layer and containing a specific polycarbonate in the upper layer is particularly effective for the above purposes. That is,

[1] An electrophotographic photoconductor containing a grafted polycarbonate resin having an organosiloxane structure having a repeating unit represented by the following general formula (1).

[0013]

[Chemical 9] (In the formula, R ₁ and R ₂ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an aryl group; R ₃ is each an alkylene group having 1 to 6 carbon atoms or alkylidene. R _{4 to} R ₇ are each a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a cycloalkane group or a phenyl group; a and b are integers of 1 to 4; m is an integer of 1 to 500. .)

[2] The electrophotographic photosensitive member according to claim 1, wherein the grafted polycarbonate resin having an organosiloxane structure has a grafted structural component represented by the following general formula (2).

[0015]

[Chemical 10] (In the formula, R _{8 to} R ₁₀ are a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group; R ₁₁ is a hydrogen atom, an alkyl group, an alkenyl group, or a substituted or unsubstituted aryl group; n is an integer of 0 to 10. ; C, d, and e represent an integer of 1 to 4.)

[3] The electrophotographic photosensitive member according to claim 1 or 2, wherein the grafted polycarbonate resin having an organosiloxane structure contains a repeating unit having a structure represented by the following general formula (3).

[0017]

[Chemical 11] (In the formula, R ₁₂ and R ₁₃ are a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group each having 1 to 4 carbon atoms, or an aryl group; A is a simple bond, —O—, —S
-, - CO -, - SO -, - SO 2 -, each substituted, unsubstituted, linear, branched, or cyclic alkylidene group or an alkylene group,

[0018]

[Chemical 12] R ₁₄ and R ₁₅ are each a substituted or unsubstituted alkyl group or aryl group; f and g each represent an integer of 1 to 4. )

[4] The electrophotographic photosensitive member according to claim 1, 2 or 3, wherein a grafted polycarbonate resin having an organosiloxane structure is contained in the outermost surface layer on the conductive support.

[5] An electrophotographic photosensitive member comprising a conductive support, and a charge generation layer containing at least a charge generation substance and a charge transport layer containing a charge transport substance, which are laminated in this order. Is composed of a plurality of constituent layers, and the constituent layer of the plurality of constituent layers located on the side farther from the conductive support contains a grafted polycarbonate resin having an organosiloxane structure. 4. The electrophotographic photosensitive member according to any one of to 4.

[6] The constitutional layer containing a grafted polycarbonate resin having an organosiloxane structure further contains a charge transporting substance represented by the following general formula (4) or (5). Electrophotographic photoreceptor.

[0022]

[Chemical 13] [In each formula, R ₁₆ and R ₁₇ each represent a substituted or unsubstituted alkyl group or aryl group, and the substituent is a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or a substituted amino group. . , R ₁₈ and R ₁₉
Represents a hydrogen atom, a substituted or unsubstituted aryl group, and the substituent is a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or a substituted amino group.

Ar ₁ is a substituted or unsubstituted arylene group, A
r ₂ represents a substituted or unsubstituted aryl group, and each substituent represents a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or a substituted amino group.
R ₂₀ and R ₂₁ are hydrogen atom, halogen atom, alkyl group or alkoxy group; R _{22 to} R ₂₅ are hydrogen atom, halogen atom, alkyl group, alkoxy group or substituted amino group; h, i, j and k are 1 Or represents 2. ]

[7] A is a mere bond, or

[0025]

[Chemical 14] (Z is an atomic group necessary for forming a cycloalkane ring having two or more substituents selected from an alkyl group, a cycloalkyl group and an aryl group or an unsubstituted group). The electrophotographic photosensitive member described.

[8] The electrophotographic photosensitive member according to claim 3 or 7, wherein the structural unit represented by the general formula (1) is a structural unit represented by the following general formula (1-I).

[0027]

[Chemical 15] (In the formula, R ₁ , R ₂ , a, and b are the same as those in the general formula (1).
₂₆ is an alkylene _{group; R 27, R 28, R} 2 9, R 30
Each is a substituted or unsubstituted alkyl group or aryl group; r,
s is 10 or a positive integer, and 10 ≦ (r + s) ≦ 5
The relationship of 00 is satisfied. However,

[0028]

[Chemical 16] Do not have the same units. )

[0029]

[9] Content of grafting component is 0.0
9. The electrophotographic photosensitive member according to claim 1, which contains 1 to 3% by weight of a grafted polycarbonate resin having an organosiloxane structure.

The resin of the present invention will be described in detail below. The resin of the present invention is roughly classified into a component having an organosiloxane structure, a structural component having a structure contributing to grafting, and other components used as necessary. Each component will be described in detail below.

The component having an organosiloxane structure is
It is a component represented by the following general formula (1).

[0032]

[Chemical 17] In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an aryl group, and R ₃ each represents an alkylene group having 1 to 6 carbon atoms or Represents an alkylidene group, R _{4 to} R ₇ each represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms) or a phenyl group, and a and b each represent 1 to 1; 4, m represents an integer of 1 to 500.
When the value of m is less than 1, there is no effect of improving the physical properties by introducing a siloxane structure, while when it exceeds 500, the production becomes difficult, and it is preferably 10 to 400, particularly preferably 20 to 300. Further, in the general formula (1), a component which is a structural unit represented by the following general formula (1-I) is preferable.

[0033]

[Chemical 18] In the formula, R ₁ , R ₂ , a and b have the same meanings as in formula (1), R ₂₆ is an alkylene group, preferably an alkylene group having 1 to 6 carbon atoms, R ₂₇ , R ₂₈ ,
R ₂₉ and R ₃₀ are each a substituted or unsubstituted alkyl group or aryl group, preferably a methyl group or a phenyl group, or
R ₂₈ is preferably a fluorine atom-substituted alkyl group having 1 to 15 carbon atoms, particularly preferably a fluorine atom-substituted alkyl group having 1 to 10 carbon atoms, and r and s are O or a positive integer,
The relationship of 10 ≦ (r + s) ≦ 500 is satisfied.

However,

[0035]

[Chemical 19] And never have the same unit.

R ₂₈ is --CH ₂ CH ₂ --R ₂₈ '(R
₂₈ 'is also preferably a perfluoroalkyl group having 1 to 15 carbon atoms.

As the component having a structure that contributes to grafting in the present invention, any component can be used as long as it is a component that grafts the polycarbonate resin according to the present invention, but is preferably represented by the following general formula (2). It is what is done.

[0038]

Embedded image In the formula, R _{8 to} R ₁₀ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, preferably a hydrogen atom, and an alkyl group or an alkoxy group each having 1 to 4 carbon atoms, and R 8
₁₁ is a hydrogen atom, an alkyl group, an alkenyl group, a substituted or unsubstituted aryl group, preferably a hydrogen atom, having 1 carbon atom
To 4 are alkyl groups, phenyl groups and hydroxyphenyl groups, n is an integer from 0 to 10 and c, d and e are integers from 1 to 4.

The resin of the present invention may basically have a repeating unit having the above-mentioned two kinds of components, or may be a copolymer having other components. In particular, the following general formula (3) It is preferable that it is a copolymer of at least 3 types of components which has the component of the repeating unit of the structure shown by (4).

[0040]

[Chemical 21] In the formula, R ₁₂ and R ₁₃ represent a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group each having 1 to 4 carbon atoms, or an aryl group (preferably a phenyl group), A is a simple bond, —O— , -S-, -CO-, -SO-,-
SO ₂ -, each substituted, unsubstituted linear or cyclic alkylidene group or an alkylene group, preferably a single _{bond, -O -, - SO 2 -} , alkyl group having 1 to 4 carbon atoms, a substituted, unsubstituted Represents a cyclohexylidene group and an alkylene group having 1 to 4 carbon atoms.

The resin of the present invention may further contain a polycarbonate structural component other than the above as a structural component, and may also contain a polymer structural component other than the polycarbonate structural component.

One of the characteristics of the resin of the present invention is that it is a grafted resin. In the resin of the present invention, the ratio of grafting is arbitrary, but the objects of the present invention are From the viewpoint of being sufficiently and surely achieved, the grafting component is preferably 0.01 to 3% by weight based on the whole resin.

The component represented by the general formula (1) which is one of the essential components is similarly 1 to 50% by weight based on the whole resin, and the other components, particularly the component represented by the general formula (3) are the same. Further, the resin is preferably 5 to 99% by weight based on the whole resin.

Typical examples of the monomers of the respective components constituting the resin of the present invention are shown below.

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

[0049]

[Chemical formula 26] Next, specific examples of these copolymers are as follows. Representative specific examples of the monomer of the grafted structural component will be given below.

[0050]

[Chemical 27]

[0051]

[Chemical 28] Typical other examples of the monomer of the structural component represented by the general formula (3) are shown below.

[0052]

[Chemical 29]

[0053]

[Chemical 30]

[0054]

[Chemical 31] The polycarbonate resin of the present invention can be generally produced by reacting a corresponding divalent phenol compound and a trivalent or higher valent phenol compound as a grafting component with a carbonic acid ester forming compound.

In this reaction, a carbonyl dihalide such as phosgene, a haloformate such as a chloroformate or a carbonate compound is used as a carbonate forming compound, and a polycondensation reaction is carried out in the presence of an appropriate acid binder. Alternatively, it is carried out by a method such as performing an ester conversion reaction using bisaryl carbonates as a carbonic acid ester forming compound.

The above synthesizing method is described in, for example, Japanese Patent Laid-Open No. 6-136.
No. 108 publication, the resin of the present invention can be synthesized with reference to the publication.

The following representative synthetic examples are shown below. Synthesis Example-1 Monomer [1-1] 32.52 g (0.01 mol) Monomer [3-1] 45.6 g (0.2 mol) Monomer [2-1] 0.31 g (0.001 mol) Concentration 700 ml of 8% aqueous sodium hydroxide solution, 500 ml of methylene chloride, 0.15 g of p-tert-butylphenol as a terminal stopper (molecular weight regulator), and 3 ml of 10% triethylamine aqueous solution as a catalyst were introduced into a reactor with a baffle plate to carry out reaction. Phosgene was added at a rate of 600 ml / min with vigorous stirring while maintaining the temperature at around 10 ° C.
Blowing for 5 minutes, the polycondensation reaction was performed. After completion of the reaction, the organic phase was diluted with 1 liter of methylene chloride, washed with water, diluted hydrochloric acid and water in this order, and then poured into methanol to obtain the resin of the present invention (viscosity average molecular weight 3.4 × 10 ⁴ ). Obtained.

Composition analysis of the obtained resin was confirmed by hydrolysis separation, chromatographic separation, and MAS analysis to be the polycarbonate of the specific example (P-1). Synthesis Example-2 Monomer [1-13] 46.5 g (0.003 mol) Monomer [3-2] 51.2 g (0.2 mol) Monomer [2-1] 0.31 g (0.001 mol) Above The mixture of monomers was 800 ml of an aqueous solution of sodium hydroxide having a concentration of 8%, 550 ml of methylene chloride, 0.15 g of p-tert-butylfettle as a terminal stopper (molecular weight regulator), and 3 ml of a 10% triethylamine aqueous solution as a catalyst in a reactor with a baffle plate. At a reaction temperature of 10
While maintaining the temperature at around ℃, phosgene was added to 60 with vigorous stirring.
The polycondensation reaction was carried out by blowing for 15 minutes at a rate of 0 ml / min. After completion of the reaction, the organic phase was diluted with 1 liter of methylene chloride, washed with water, diluted hydrochloric acid and water in this order, and then poured into methanol to obtain the resin of the present invention (viscosity average molecular weight 2.
5 × 10 ⁴ ) was obtained.

The composition analysis of the obtained resin was confirmed to be the polycarbonate of Concrete Example (P-9) by hydrolysis separation, chromatographic separation and MAS analysis.

The molecular weight of the resin of the present invention is preferably 10,000 to 10 in terms of viscosity average molecular weight (Mv).
30,000, particularly preferably 10,000 to 70,000
Those in the range of 00 are suitable. The viscosity average molecular weight (Mv) referred to herein is a value obtained from ηsp measured at 20 ° C. using a methylene chloride solution containing 6.0 g / l of a polymer by the following formulas (3) and (4).

Ηsp / C = [η] (1 + K′ηsp) ... (3) [η] = K (Mv) α ... (4) C: Polymer concentration (g / L), K ′ = 0.28, K =
1.23 × 10 ⁻³ α = 0.83, [η]: Intrinsic viscosity, Mv: Viscosity average molecular weight Next, typical examples of the resin of the present invention will be given.

[0062]

[Chemical 32]

[0063]

[Chemical 33]

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

[Chemical 38] The electrophotographic photoreceptor according to the present invention may be any electrophotographic photoreceptor in which a photosensitive layer is provided on a conductive support, and particularly, a charge generation layer (CGL) containing a charge generation material (CGM) and a charge transport layer. Charge transport layer (CT) containing substance (CTM)
A function-separated electrophotographic photosensitive member provided separately from L) is preferably used. The resin of the present invention is used in any constituent layer constituting these electrophotographic photoreceptors. However, from the viewpoint of effectively achieving the objects of the present invention, it is preferably used for the outermost layer, and particularly preferably used in the constitution described in detail below.

That is, in FIG. 1, C is placed on the conductive support.
GL2 is provided, and then CTL3 is provided. In this case, C
TL3 is a plurality of CTLs of the CTL lower layer side constituent layer 4 and the CTL upper layer side constituent layer 5. 2 shows the conductive support 1 and CG.
An intermediate layer 6 such as an adhesive layer and a barrier layer is provided in the middle of L2. The resin of the present invention is used in any of the constituent layers in the electrophotographic photoreceptors of FIGS. 1 and 2, but preferably in CTL3, particularly preferably in CTL upper constituent layer 5.
Used for

Further, in the electrophotographic photosensitive member according to the present invention, a protective layer may be provided on the photosensitive layer, and in this case, the resin of the present invention is preferably contained in this protective layer.

The resin of the present invention is usually used as a binder, and when it is used for CTL and CGL, it is usually used for CT.
It is used in the same ratio as that of M, CGM and the binder.

For example, when used for CTL, CTM
The content of the resin in the resin of the present invention is 30% by weight or more, preferably 50 to 300% by weight. In particular, the resin of the present invention can have a very large CTM content of, for example, 300% by weight, so that the photocharge injection capability from the CTL can be increased.

Next, the CTL according to the present invention will be described. In the present invention, the CTL is preferably composed of at least two layers, and in this case, the outermost CTL (5 in FIG. 1).
Examples include a charge transport material (CTM) and the resin of the present invention, and in some cases, the resin of the present invention and other conventional polycarbonates (for example, JP-A-56-119135 and JP-A-1-2509).
No. 81 etc. polycarbonate), and the binder-side CTL (4 in FIG. 1) is dissolved with another binder resin, preferably the above-mentioned normal or inventive polycarbonate in a solvent. It can be formed by a method in which the dispersed solution or dispersion is applied onto CGL and dried.

In the photoreceptor of the present invention, pyrazoline compounds, hydrazone compounds, stilbene compounds, triphenylamine compounds, benzine compounds, oxazole compounds, indole compounds, carbazole compounds and the like are used as CTM.

C which is preferably used with the resins according to the invention
Typical examples of TM are compounds represented by the general formulas [II] to [X] described in Japanese Patent Application No. 5-240801, and specific examples of the compound are described in Japanese Patent Application No. 5-240801, 58.
Pp.-64. More preferably, it is a CTM represented by the following general formulas (4) and (5).

[0076]

[Chemical Formula 39] [R ₁₆ and R ₁₇ represent a substituted or unsubstituted alkyl group or aryl group, and examples of the substituent include an alkyl group, an alkoxy group, a substituted amino group, a hydroxyl group, a halogen atom and an aryl group.

Ar ₁ is a substituted or unsubstituted arylene group, A
r ₂ : represents a substituted or unsubstituted aryl group, and as the substituent, an alkyl group, an alkoxy group, a substituted amino group, a hydroxyl group,
A halogen atom and an aryl group.

R ₁₈ and R ₁₉ represent a hydrogen atom, a substituted or unsubstituted aryl group, and examples of the substituent include an alkyl group, an alkoxy group, a substituted amino group, a hydroxyl group, a halogen atom and an aryl group. ]

[0079]

[Chemical 40] [In the formula, R ₂₀ , R ₂₁ are hydrogen atoms, halogen atoms, alkyl groups or alkoxy groups; R _{22 to} R ₂₅ are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or substituted amino groups; h, i, j , K represents 1 or 2. The typical examples of CTM preferably used in the present invention are shown below.

[0080]

Embedded image

[0081]

[Chemical 42] Of the CTLs, the film thickness of the outermost CTL is 1.0 to 10 μm.
It is preferably m.

The CTL on the side of the conductive support contains the same or different CTM as that added to the outermost layer, and the content of the charge transport material in the layer is 30% by weight or more, more preferably 50 to 50%. It is preferably 300% by weight.

A method for forming the charge transport layer will be described. A coating solution is prepared in the same manner as the charge generation layer, and this is coated to form a charge transport layer. For the coating, dip coating, spray coating, bead coating, or the like may be used as in the case of the intermediate layer and the charge generating layer.

If necessary, the CTL contains an antioxidant,
It may contain various additives such as a sensitizer. The CTL has a thickness of 10 to 60 μm, preferably 10 to 45 μm. In the case of the dispersion type photosensitive layer, it is preferable that the above charge generating substance is dispersed in the charge transport medium containing the resin of the present invention in the above blending ratio. In that case, the particle size must be sufficiently small, and the particle size is preferably 1 μm or less, more preferably 0.5 μm or less. If the amount of CGM dispersed in the photosensitive layer is too small, sufficient sensitivity cannot be obtained, and if it is too large, there are adverse effects such as a decrease in charging property and a decrease in sensitivity.
It is used in the range of 50% by weight, more preferably in the range of 1 to 20% by weight. The thickness of the photosensitive layer is usually 5 to 50 μm,
It is more preferably used in the range of 10 to 45 μm. Also in this case, known plasticizers for improving film-forming properties, flexibility, mechanical strength, etc., additives for controlling residual potential,
Additives such as a dispersion aid for improving dispersion stability, a leveling agent for improving coatability, and a surfactant may be used.

In the present invention, as CGL, a dispersion liquid in which CGM is dispersed alone or together with a suitable binder resin in a suitable dispersion medium is applied on a conductive support or an intermediate layer if necessary, and dried. It can be formed by a method, a vacuum deposition method, or the like.

In the photoconductor of the present invention, the pigments represented by the following representative examples of CGM are used. (1) Azo pigments such as monoazo pigments, bisazo pigments, triazo pigments, metal complex salt azo pigments, etc. (2) Perylene pigments such as perylene anhydride, perylene imide, etc. (3) Anthraquine derivatives, anthanthrone derivatives,
Polycyclic quinone pigments such as dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives and isobiolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo derivatives (5) Phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine More detailed charge With respect to the generating substance, as the charge generating substance preferably used in the present invention, a polycyclic quinone pigment described in JP-A-59-184353, more preferably a dibromoanthanthrone pigment is preferable.

Alternatively, a bisazoazo pigment described in JP-A-2-20877, and more preferably a fluorenone type bisazo pigment represented by the general formula [III] described in the specification is preferable. Alternatively, a halogen-substituted perylene pigment described in JP-B-3-26384, an asymmetric perylene pigment described in JP-A-62-54267, and JP-A-54-126036.
No. 58-152247, No. 59-31957,
JP-A-2-251858, 4-62560, 5
No. 6014, and more preferably the bisimidazopyridonoperylene pigment described in Japanese Patent Application No. 3-279764.

Alternatively, α-type titanyl phthalocyanine described in JP-A-61-239248, 62-67094.
-Type titanyl phthalocyanine described in No. 63-366
C-type titanyl phthalocyanine described in JP-A-2-30
Type 9 titanyl phthalocyanine described in No. 9362 is ant,
More preferably, Y described in Japanese Patent Application No. 62-173640.
Type titanyl phthalocyanine is good.

As the solvent or dispersion medium used for forming the charge generation layer, any known solvent or dispersion medium may be used.

Further, at least the CTL containing CTM described below can be formed in the same manner as the above CGL, and any binder resin can be used for forming CGL or CTL described below.
It is preferable to use a film-forming high molecular polymer which is hydrophobic, has a high dielectric constant, and is electrically insulating. Examples of such a high molecular weight polymer include polycarbonate, polyethylene, methacrylic acid, acrylic resin, polyvinyl chloride, polyvinylidene chloride polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer vinyl chloride. -Vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral or polyvinyl formal. Any binder resin such as can be used alone or as a mixture of two or more kinds.

In the CGL thus formed, the weight ratio of CGM and binder is preferably 10
It is 0: 0 to 1000.

If the content ratio of CGM is less than this range, the photosensitivity is low and the residual potential is increased, and if it is more than this range, the dark decay is increased and the receptive potential is decreased.

When CTM is contained in CGL, the weight ratio of CGM and CTM is from 10: 0 to 1
It is preferably 0: 1000, particularly preferably 1
It is 0: 0 to 10: 100.

The thickness of the charge generation layer formed is preferably 0.01 to 10 μm.

In the present invention, when an intermediate layer is provided between the conductive support and the charge generating layer, the thickness of the intermediate layer is 0.01 to 0.15 μm, preferably 0.05 to 0.1 μm.
The range is 3.0 μm. If it is less than 0.01 μm, the injection of charges from the support to the photosensitive layer cannot be prevented. In addition, pinholes are easily generated on the photoconductor due to the unevenness of the support. If it exceeds 15 μm, the residual potential of the photosensitive layer cannot be effectively removed.

Further, the binder used in the intermediate layer is selected in consideration of electric resistance, environment resistance, adhesiveness to other layers, insolubility in solvents of other layers, and the like.

Binder resin used for the intermediate layer, as a material, metal oxide such as aluminum oxide and indium oxide, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin , Alkyd resin, polycarbonate resin, polyamide resin, silicone resin, melamine resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin and the like can be used, A coating solution in which these polymer substances are dissolved and dispersed is coated on the conductive support to form an intermediate layer.

Conventionally, when the organic photoconductive photosensitive layer is coated and formed, various coating methods such as dip coating, blade coating, spin coating, beam coating and spiral coating have been used, but the coating method is easy and Since a smooth coating film can be easily obtained, the dip coating method of dipping and coating an object to be coated in a tank filled with a large amount of coating liquid is most popular.

However, in the dip coating method, the lower layer is dissolved when the photosensitive layers are laminated and coated. That is, if the lower layer is dissolved during application of the surface layer, the coating film is destroyed and the functions of the surface layer and the lower layer are lost, and the performance of the photoreceptor is not exhibited. Also, when unevenness, streaks, spots, irregularities, etc. occur during application of the surface layer, the electrophotographic performance is partially or locally different, image unevenness occurs, the image quality deteriorates, and photoelectric and functional durability Also deteriorates the electrophotographic performance. Further, in the dip coating method, since the objects to be coated are dipped one by one in a tank containing a large amount of the coating solution, the coating solution is wasted much,
There is also a problem that the coating efficiency is poor and the coating liquid in the tank changes between the initial stage and the latter stage of the coating process to cause variations in electrophotographic performance.

Therefore, as in the present invention, if at least the outermost layer is coated with a circular amount-regulating type coating machine (for example, a circular slide hopper coating machine), the above problems can be solved, and the outermost layer and the other constituent layers have different charges. When a transport substance is used, it is also an effective means against the problem of contamination due to elution of the lower layer charge transport substance into the outermost layer coating liquid.

Regarding the characteristics of the coating principle of the circular amount control type coating machine, Japanese Patent Application Laid-Open No. 60-95440 and Japanese Patent Application No. 3-90250.
Issue.

The conductive support 1 used in the photoconductor according to the present invention includes a metal plate containing an alloy, a metal drum or a conductive polymer, aluminum containing a conductive compound such as indium oxide or an alloy, palladium, Paper, plastic film, etc. which are made conductive by applying a thin metal layer of gold or the like, vapor deposition or lamination are mentioned. As the intermediate layer 5 such as the adhesive layer or the barrier layer, in addition to the polymer used as the binder resin, an organic polymer such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, polyamide, or aluminum oxide is used.

An electrophotosensitive material having two or more layers of CTLs according to the present invention and containing a polycarbonate resin having a specific polysiloxane as a side chain in at least the outermost layer has no adverse effect on electrical characteristics and the like, and is exposed. It is extremely effective for extending the life of the body and is useful for high-speed copying machines and printers.

[0104]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 As a conductive support, a mirror-finished diameter of 80 mm,
An aluminum support with a length of 355 mm was used.

Photoreceptor 1-1 (for Example 1-1) The following intermediate layer coating solution was applied onto the support by dip coating so that the film thickness after drying was 0.2 μm. Layers were formed. [Intermediate layer coating liquid] Polyamide (manufactured by Toray Industries, Inc.) 27 g Methanol 1800 ml Next, the following composition was applied onto the above intermediate layer by a sand mill.
The CGL coating liquid prepared by dispersing for 0 hours was applied by dip coating so that the film thickness after drying was 1.5 μm, and then CGL was applied.
Was formed. [CGL coating liquid] CGM-1 30 g Petitral resin Elex B (BX-L Sekisui Chemical Co., Ltd.) 10 g Methyl ethyl ketone 1800 ml Then, the following CTL coating liquid A was applied by dip coating so that the film thickness after drying would be 20 μm. , CTL on the support side was formed. [CTL coating liquid A] T _1-10 500 g Polycarbonate (Z300 manufactured by Mitsubishi Gas Chemical Co., Inc.) 560 g was mixed with 1,2-dichloroethane (2800 m).
Dissolved in 1.

Next, the following CTL coating liquid B was applied by a circular amount regulating type coating machine with a slide angle of 50 ° so that the film thickness after drying would be 7 μm to form a CTL surface region side constituent layer. Photoconductor No. Is set to 1. (For Photoreceptor 1) [CTL Coating Liquid B] CTM-1 350 g Polycarbonate (Exemplified Compound P-7) 700 g A mixture of 10,2-dichloroethane 2800
Dissolved in ml.

In the same manner as in Example 1-1, C as shown in Table 1 was used.
Photoreceptors of GL, CTL lower layer and CTL upper layer were prepared. Photoconductor No. Is 1-2 to 1-9.

Photoreceptor No. 1-10 (for Comparative Example 1-1) A photoreceptor was prepared in the same manner as the photoreceptor except that the support side CTL of the photoreceptor 1-1 was used in a single layer of 27 μm. Photoconductor No. 1-
It is assumed to be 10.

Photoreceptor No. 1-11 (for Comparative Example 1-2) Photosensitive member No. 1 except that the CTL on the outermost layer side of the photosensitive member 1-5 was changed as shown in Table 1. It was made in the same manner as 1-5. Photoconductor No. 1-11. <Evaluation of Electrophotographic Photoreceptor> The electrophotographic photoreceptor obtained as described above is used as a copying machine U-BIX404 manufactured by Yunika Co., Ltd.
5 was used to perform the characteristic evaluation described below. The results are shown in Table 1. [Evaluation of electrical characteristics and repetitive characteristics] The above copying machine was remodeled and equipped with a surface electrometer, and the first, 100, and 100 times of the process of charging → exposure → static elimination were repeated.
The 000th charge potential was measured and evaluated.

As a result, when the fluctuation of the charging potential of the photosensitive member is less than 100 V between the first time and the 100,000th time, ◯, 100-1.
99V was designated as Δ, and exceeding 200V was designated as x. [Abrasion resistance evaluation] The abrasion resistance of the photoconductor was evaluated by the amount of change in the photoconductor film thickness before and after the actual copying test of 50,000 copies. The film thickness of the photoconductor is EDDY560 manufactured by Fischer.
Measured at C.

[0112]

[Table 1]

From Table 1, it is possible to improve the sensitivity, the amount of wear, the adhesiveness, the blade flipping and the like by using the resin of the present invention with two layers of CTL. CTL or CT of the resin of the present invention
When used as a CTL binder of L single layer, the sensitivity is improved by increasing the amount of CTM in CTL, but the adhesiveness with the CGL interface is deteriorated.

[0114]

[Chemical 43]

[0115]

[Chemical 44] Example 2 As the conductive support, a mirror-finished diameter of 80 mm,
An aluminum support with a length of 355 mm was used.

Photoreceptor No. 2-1 (For Example 2-1) An intermediate layer was formed by dip-coating the following intermediate coating solution on the support so that the film thickness after drying was 0.2 μm. [Intermediate layer coating liquid] Polyamide (manufactured by Toray Industries, Inc.) 27 g Methanol 1800 ml Next, the following composition was applied onto the above intermediate layer by a sand mill.
The CGL coating liquid prepared by dispersing for 0 hours was applied by dip coating so that the film thickness after drying was 1.5 μm, and then CGL was applied.
Was formed. [CGL Coating Liquid] CGM-1 30 g Butyral resin Elex B (BX-L Sekisui Chemical Co., Ltd.) 10 g Methyl ethyl ketone 1800 ml Then, the following CTL coating liquid A was applied by dip coating so that the film thickness after drying would be 20 μm. , CTL on the support side was formed. [CTL coating liquid A] CTM-2 500 g Polycarbonate (Z200 manufactured by Mitsubishi Gas Chemical Co., Inc.) 560 g was mixed with 1,2-dichloroethane 2800 m.
Dissolved in 1.

Next, the following CTL coating liquid B was applied by a circular amount regulating type coating machine with a slide angle of 50 ° so that the film thickness after drying would be 7 μm to form a CTL surface region side constituent layer. Photoconductor No. To 2-1 (Example 2)
-1). [CTL coating liquid B] CTM-1 350 g Polycarbonate (exemplary compound P-2) 700 g of a mixture of 1.2-dichloroethane 2800 m
Dissolved in 1.

Photoreceptor No. 2-2-2-5 (Example 2-
For 2 to 2-5) CGL and CTL as shown in Table 2 in the same manner as in Example 2-1.
A lower layer and an upper layer of the CTL were prepared. Each photoconductor N
o. 2-2 to 2-5.

Photoreceptor 2-6 (for Comparative Example 2-1) A photoreceptor 2-5 was prepared in the same manner as the photoreceptor 2-5 except that the support side CTL of the photoreceptor 2-5 was used in a single layer of 27 μm. Photoconductor N
o. Is set to 2-11.

Photoreceptor 2-12 (for Comparative Example 2-2) The same procedure as in Photoreceptor 2-5 except that the binder in CTL on the outermost layer side of Photoreceptor 2-5 was used in Comparative 1 with a layer thickness of 7 μm. It was made. Photoconductor No. 2-7.

[0121]

[Table 2]

[0122]

EFFECTS OF THE INVENTION According to the present invention, abrasion resistance and printing durability are excellent and durability is high, and potential stability is lowered by repeated use.
It is possible to provide an electrophotographic photoreceptor in which the increase in residual potential and the decrease in photosensitivity are small.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a configuration example of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a cross-sectional view showing a configuration example of an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 1 Dielectric Support 2 Charge Generation Layer 3 Charge Transport Layer 4 Charge Transport Layer Lower Composition Layer 5 Charge Transport Layer Upper Composition Layer 6 Intermediate Layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03G 5/06 313

Claims (9)

[Claims] 1. An electrophotographic photoreceptor containing a grafted polycarbonate resin having an organosiloxane structure having a repeating unit represented by the following general formula (1). [Chemical 1] (In the formula, R ₁ and R ₂ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or an aryl group; R ₃ is each an alkylene group having 1 to 6 carbon atoms or alkylidene. R _{4 to} R ₇ are each a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a cycloalkane group or a phenyl group; a and b are integers of 1 to 4; m is an integer of 1 to 500. .) 2. The electrophotographic photoreceptor according to claim 1, wherein the grafted polycarbonate resin having an organosiloxane structure has a grafted structural component represented by the following general formula (2). [Chemical 2] (In the formula, R _{8 to} R ₁₀ are a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group; R ₁₁ is a hydrogen atom, an alkyl group, an alkenyl group, or a substituted or unsubstituted aryl group; n is an integer of 0 to 10. ; C, d, and e represent an integer of 1 to 4.) 3. The electrophotographic photoreceptor according to claim 1, wherein the grafted polycarbonate resin having an organosiloxane structure contains a repeating unit having a structure represented by the following general formula (3). [Chemical 3] (In the formula, R ₁₂ and R ₁₃ are a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group each having 1 to 4 carbon atoms, or an aryl group; A is a simple bond, —O—, —S
-, - CO -, - SO -, - SO 2 -, each substituted, linear unsubstituted, branched or cyclic alkylidene group or an alkylene group, ## STR4 ## R ₁₄ and R ₁₅ are each a substituted or unsubstituted alkyl group or aryl group; f and g each represent an integer of 1 to 4. ) 4. The grafted polycarbonate resin having an organosiloxane structure is contained in the outermost surface layer on the conductive support, which is characterized in that
The electrophotographic photosensitive member described. 5. An electrophotographic photosensitive member comprising a conductive support, and a charge generation layer containing at least a charge generation substance and a charge transport layer containing a charge transport substance, which are laminated in this order on the conductive support. A grafted polycarbonate resin having an organosiloxane structure is contained in a constituent layer which is composed of a plurality of constituent layers and which is located on a side farther from the conductive support among the plurality of constituent layers. The electrophotographic photosensitive member according to any one of 4 above. 6. The constitutional layer containing a grafted polycarbonate resin having an organosiloxane structure further contains a charge-transporting substance represented by the following general formula (4) or (5). Electrophotographic photoreceptor. [Chemical 5] [In each formula, R ₁₆ and R ₁₇ each represent a substituted or unsubstituted alkyl group or aryl group, and the substituent is a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or a substituted amino group. . , R ₁₈ and R ₁₉
Represents a hydrogen atom, a substituted or unsubstituted aryl group, and the substituent is a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or a substituted amino group. Ar
₁ represents a substituted or unsubstituted arylene group, Ar ₂ represents a substituted or unsubstituted aryl group, and each substituent represents a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or a substituted amino group. R ₂₀ and R ₂₁ are a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; R
_{22 to} R ₂₅ are a hydrogen atom, a halogen atom, an alkyl group,
Alkoxy group or substituted amino group; h, i, j, and k represent 1 or 2. ] 7. A is a mere bond, or (Z is an atomic group necessary for forming a cycloalkane ring having two or more substituents selected from an alkyl group, a cycloalkyl group and an aryl group or an unsubstituted group). The electrophotographic photosensitive member described. 8. The electrophotographic photosensitive member according to claim 3, wherein the structural unit represented by the general formula (1) is a structural unit represented by the following general formula (1-I). [Chemical 7] (In the formula, R ₁ , R ₂ , a, and b are the same as those in the general formula (1).
₂₆ is an alkylene _{group; R 27, R 28, R} 2 9, R 30
Each is a substituted or unsubstituted alkyl group or aryl group; r,
s is 10 or a positive integer, and 10 ≦ (r + s) ≦ 5
The relationship of 00 is satisfied. However, Do not have the same units. ) 9. The content ratio of the grafting component is 0.01 to 3
9. The electrophotographic photosensitive member according to claim 1, which contains a grafted polycarbonate resin having an organosiloxane structure in a weight percentage.