JPH0862863A - Electrophotographic photoreceptor and its production - Google Patents

Abstract

PURPOSE: To obtain a photoreceptor having a high mechanical strength and excellent in potential by electrification, sensitivity and residual potential characteristics. CONSTITUTION: A photosensitive layer contg. a polycarbonate (co)polymer as a resin binder and polycarbonate diol crosslinked with a cross-linking agent and added by 1-50wt.% of the amt. of the polymer is formed on an electrically conductive substrate to obtain the objective photoreceptor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a constitution of an electrophotographic photoreceptor, particularly an organic electrophotographic photoreceptor.

[0002]

2. Description of the Related Art As an electrophotographic photoreceptor, of course, electrophotographic characteristics such as good charging characteristics and sensitivity, and small dark decay, are added. In addition, printing durability, abrasion resistance and moisture resistance after repeated use. It is also required to have good physical properties such as properties, and ozone resistance (corrosion resistance) against ozone generated during corona discharge and ultraviolet rays during exposure.

In recent years, research and development using various organic photoconductive substances as materials for the photosensitive layer of an electrophotographic photoreceptor have been actively conducted. According to such an organic electrophotographic photosensitive member, since the photosensitive layer can be formed by coating, the manufacturing cost is low, pollution and environmental pollution can be prevented, and it can be easily processed into various shapes (drum, sheet shape, etc.).

However, the organic electrophotographic photoreceptor has the following drawbacks, and there is a strong demand for solving these drawbacks.

(A) For example, when a layer is formed by binding a low molecular weight organic compound with a high molecular weight organic compound (binder), the mechanical strength is not always sufficient, and when the photoreceptor is repeatedly used, the developing blade is The surface of the photoconductor is scratched or worn due to rubbing or the like.

(B) The photoconductor is mainly used for negative charging. For example, as described in JP-A-60-247647, a thin carrier generating layer is provided on a support, and a relatively thick carrier is formed on the support. It is configured to have a transport layer.

The reason for this is that in the case of using negative charging, a hole transporting material can be used because the mobility of holes in the carrier is high, which is advantageous in terms of photosensitivity, while it has an electron transporting property. This is because there are almost no materials having excellent properties, or because they have carcinogenicity and teratogenicity, they cannot be used.

However, during negative corona discharge and during negative charging by the charger, a large amount of ozone is generated in the atmosphere, and environmental conditions deteriorate. For this reason, adsorption of ionic substances to the surface of the photoconductor and deterioration of the material of the photoconductor surface are caused, resulting in a decrease in potential during repeated use, which causes an increase in residual potential, a decrease in sensitivity, and a decrease in image quality. Lower.

(C) Since the equipment such as the electrophotographic photoreceptor is used for a long time under various conditions, it is often placed under the conditions of high temperature and high humidity. Therefore, there is a demand for a photoreceptor having high environmental resistance, but those currently being developed have not yet reached a sufficient level.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photoreceptor having high mechanical strength and excellent in charging potential characteristics, sensitivity characteristics and residual potential characteristics and having high durability even in a high temperature and high humidity environment. That is.

[0011]

The object of the present invention can be achieved by adopting any one of the following constitutions.

(1) In a photoreceptor having a photosensitive layer provided on a conductive support, the photosensitive layer contains a polycarbonate polymer or a copolymer thereof as a binder resin, and 1 to 50 parts by weight of the polymer. % Of a polycarbonate diol, and the diol is crosslinked by a crosslinking agent and contained.

(2) The electrophotographic photoreceptor according to (1), wherein the crosslinking agent is an isocyanate.

(3) The electrophotographic photosensitive member according to (1), wherein the crosslinking agent is a polyfunctional silane coupling agent.

(4) The electrophotographic photosensitive member according to (3), wherein the silane coupling agent has a fluorinated alkyl group.

(5) An electrophotographic photoreceptor according to (1), (2) or (3), wherein one of the constituents of the photosensitive layer is a siloxane polymer having a hydroxyl group at the terminal.

(6) The electrophotographic photoreceptor according to (5), wherein the siloxane polymer is crosslinked with a polycarbonate diol by a crosslinking agent.

(7) The electrophotographic photosensitive member according to (6), wherein the crosslinking agent is an isocyanate.

(8) In a photoreceptor having a photosensitive layer having at least a carrier generation layer and a carrier transport layer laminated on a conductive support, the carrier transport layer comprises a plurality of constituent layers. And at least the outermost layer thereof contains a polycarbonate polymer or a copolymer thereof as a binder resin, and contains 1 to 50% by weight of the polymer of a polycarbonate diol, the diol being crosslinked by a crosslinking agent. An electrophotographic photosensitive member characterized in that

(9) The electrophotographic photoreceptor according to (8), wherein the crosslinking agent is isocyanate.

(10) The electrophotographic photosensitive member according to (8), wherein the crosslinking agent is a polyfunctional silane coupling agent.

(11) The electrophotographic photosensitive member according to (8), wherein the crosslinking agent is a silane coupling agent, and the silane coupling agent has a fluorinated alkyl group.

(12) The electrophotographic photoreceptor according to (8), (9), or (10), wherein one of the constituent raw materials of the photosensitive layer is a siloxane polymer having a hydroxyl group at the terminal.

(13) The electrophotographic photoreceptor according to (12), wherein the siloxane polymer is crosslinked with a polycarbonate diol by a crosslinking agent.

(14) The electrophotographic photoreceptor according to (12), wherein the crosslinking agent is an isocyanate.

(15) In the method for producing a photoconductor in which a photoconductive layer is provided on a conductive support, the photoconductive layer contains a polycarbonate polymer or a copolymer thereof as a binder resin, and A method for producing an electrophotographic photosensitive member, characterized by containing up to 50% by weight of a polycarbonate diol, the diol being crosslinked by a crosslinking agent.

(16) In a photoreceptor comprising a photosensitive layer having a carrier generating layer and a carrier transporting layer laminated on at least a conductive support, the carrier transporting layer is composed of a plurality of constituent layers. And at least the outermost layer contains a polycarbonate polymer or a copolymer thereof as a binder resin, and contains 1 to 50% by weight of the polymer of a polycarbonate diol, and the diol is contained by being crosslinked by a crosslinking agent. A method for manufacturing an electrophotographic photosensitive member, comprising:

The photosensitive layer in the present invention is usually a laminate of a carrier generating substance and a carrier transporting substance together with a binder resin.

The polycarbonate diol used in the present invention has a hydroxyl group at the terminal and is preferably represented by the following general formula.

[0030]

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[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ and R ₈ each represent a hydrogen atom, a halogen atom or a lower alkyl group, w represents an integer of 2 or more, and Ra and Rb each represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group. Or a group in which Ra and Rb are bonded together to form a carbocycle or a heterocycle,
Rc and Rd each represent an alkyl group or an aryl group which may have a substituent. Next, specific compound examples are as follows, and bisphenol Z-type polycarbonate diol is particularly preferable.

[0032]

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[0033]

[Chemical 3]

The number average molecular weight is preferably about 500 to 50,000, more preferably 1,000 to 30,000.

The polycarbonate polymer used as the main binder resin preferably has the same structure as that of the diol. Therefore, as a preferable specific compound, a resin obtained by polymerizing the compounds described in "Chemical Formula 2" and "Chemical Formula 3" is typical.

The amount of the polycarbonate diol added is preferably in the range of 1 to 50% by weight based on the binder resin (polycarbonate polymer or copolymer thereof). 1% by weight
If the amount is less than the above, the effects of the present invention, that is, durability, improvement in slipperiness, etc. cannot be expected, and if the amount exceeds 50% by weight, the hardness of the coating film becomes too high and cracks or peeling from the interlayer may occur. become. A more desirable range of the addition amount of the polycarbonate diol is 5 to 40% by weight.

On the other hand, the desirable range of addition amount of the crosslinking agent is 10 to 100 mol% with respect to the polycarbonate diol.

As the cross-linking agent preferably used in the present invention, isocyanate type ones, especially so-called aromatic polyisocyanates are preferable. Examples of these desirable compounds include the following.

[0039]

[Chemical 4]

[0040]

[Chemical 5]

[0041]

[Chemical 6]

[0042]

[Chemical 7]

[0043]

Embedded image

[0044]

[Chemical 9]

The cross-linking agent preferably used in the present invention is further referred to as a polyfunctional silane coupling agent. This contains a large amount of polyfunctional silane compounds having two or more alkoxy groups in the molecule, and representative examples include the following.

[0046]

[Chemical 10]

As the polyfunctional silane coupling compound preferably used for improving the sliding performance of the surface of the photoconductor, a compound having a fluorinated alkyl group, particularly a compound having a fluorinated alkyl group having 4 or more carbon atoms is preferable.

[0048]

[Chemical 11]

Further, as a compound which is preferably combined with a polycarbonate diol by using a separate cross-linking agent to improve the sliding performance of the surface of the photosensitive member, a polysiloxane polymer having a hydroxyl group is used. Typical examples are the following phenol-modified polysiloxanes and carbinol-modified polysiloxanes having terminals.

[0050]

[Chemical 12]

[0051]

That is, these resins are excellent in mechanical strength, scratch resistance, abrasion resistance, printing durability, and have good charging performance. In particular, the surface of the forming layer has a high surface strength, a low dynamic friction coefficient, good transparency and insulating properties, and excellent compatibility with a carrier transport substance.

The "constituent layer of the carrier transport layer" is preferably two layers or three or more layers.

Next, the general formula constitution of the photoreceptor of the present invention is shown in FIG.
For example.

In FIG. 1, the photosensitive member (a) has a carrier generating layer 2 provided on a conductive support 1 and a carrier transporting layer 3 composed of constituent layers 3A and 3B provided on the carrier generating layer 2. Is. In the photosensitive member (b), the conductive support 1 is formed by providing the conductive layer 1B on the substrate 1A. In the photoconductor of (C), the surface protection layer 5 is provided on the photoconductor. In the photoreceptor of (d), the intermediate layer or the subbing layer 6 is provided between the carrier generating layer 2 and the conductive support 1 in the photoreceptor of (a).
Is provided.

Carrier transport layer constituent layer ((a) on the uppermost layer side)
In the examples of (d) to (d), the content ratio (weight ratio: carrier transport substance / binder substance) of the carrier transport substance to the binder substance in the constituent layer 3B) is 75% by weight or less, and more preferably 5 to 75% by weight. desirable. As a result, the film forming strength can be increased and the carrier transporting ability is not hindered.

Carrier transport layer constituting layer on the lowermost layer side ((a)
In the examples (d) to (d), the content ratio of the carrier transport material to the binder resin in the constituent layer 3A) is preferably 30% by weight or more, and more preferably 30 to 300% by weight. This makes it possible to increase the ability to inject photocarriers from the carrier generation layer. What is worth mentioning is that the content ratio of the carrier transport substance can be made very large, for example, 300% by weight,
This is possible because the film forming strength of the carrier transport layer constituting layer on the surface region side of the photoconductor is increased.

The lower constituent layer 3A preferably has a thickness of 5 to 50 μm, more preferably 5 to 30 μm. The upper constituent layer 3B preferably has a thickness of 0.1 to 10 μm, and a thickness of 0.5 to 5 μm.
It is more preferable that the thickness is μm.

The thickness of the carrier generating layer is preferably 0.01 μm to 10 μm, more preferably 0.1 to 5 μm. The thickness of the protective layer is preferably 2 μm or less, more preferably 1 μm or less.

Carrier transport layer constituent layer ((a) on the uppermost layer side)
In the examples of (d) to (d), the binder material used in the carrier transport layer below the constituent layer 3B) may be a single binder or a combination of other binders when forming the carrier transport layer. Although any binder can be selected, a polymer that is soluble in a solvent and has a film-forming ability is preferable. Examples of such polymers include, but are not limited to, the following.

Polycarbonate resin Polycarbonate Z resin Acrylic resin Methacrylic resin Polyvinyl chloride Polyvinylidene chloride Polystyrene Styrene-butadiene copolymer Polyvinyl acetate Polyvinyl formal Polyvinyl butyral Polyvinyl acetal Polyvinylcarbazole Styrene-alkyd resin Silicon resin Silicon-alkyd resin Silicon-butyral resin Polyester Polyurethane Polyamide Epoxy resin Phenolic resin Vinylidene chloride-acrylonitrile copolymer Vinyl chloride-vinyl acetate copolymer Vinyl chloride-vinyl acetate-maleic anhydride copolymer Among these resins, polycarbonate resin or polycarbonate Z resin is most preferable.

The carrier-generating substance used in the electrophotographic photosensitive member of the present invention is a phthalocyanine compound, specifically, a mixture of a titanyl phthalocyanine and other phthalocyanines such as A-type, B-type and Y-type crystal type titanyl phthalocyanine. And various metal phthalocyanines represented by non-metal phthalocyanines such as X-type and τ-type and copper phthalocyanine, naphthalocyanines, and other porphyrin derivatives, azo compounds, perylene dyes such as imidazoleperylene and bisimidazopyridonoperylene. , Polycyclic quinone dyes such as ansanthuron and anthraquinone, perinone dyes, pyrylium compounds and eutectic complexes of pyrylium compounds, azurenium compounds and squarylium compounds.

Specific examples of the azo compound used in the present invention include compounds represented by the following "Chemical Formula 13" as described in JP-A No. 2-20877.

[0063]

[Chemical 13]

The bisimidazopyridonoperylene used in the present invention is represented by the general formula (2) or the general formula (3).

[0065]

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However, in the general formulas (2) and (3), Z represents an atomic group necessary for forming a substituted or unsubstituted divalent aromatic ring. Preferred examples of Z include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyridine ring, a pyrimidine ring, a pyrazole ring and an anthraquinone ring. Of these, a benzene ring and a naphthalene ring are preferable, and a benzene ring is particularly preferable. Z may or may not have a substituent, but an unsubstituted one is particularly preferable. As the substituent of Z, alkyl, alkoxy, aryl, aryloxy, acyl,
Acyloxy, amino, carbamoyl, halogen, nitro, cyano and the like can be mentioned, but an alkyl group is preferable.

The following general formulas (2) and (15) and (16)
Specific examples of the compound represented by (3) are shown below.

[0068]

[Chemical 15]

[0069]

Embedded image

Various carriers can be used as the carrier transporting material used in the electrophotographic photosensitive member of the present invention. Typical examples thereof include oxazole, oxadiazole, thiazole, thiadiazole and imidazole. A compound having a nitrogen-containing heterocyclic nucleus and a condensed ring nucleus thereof, a polyarylalkane compound, a pyrazoline compound, a hydrazone compound, a triarylamine compound, a styryl compound, a poly (bis) styryl compound, a styryl Triphenylamine compound, β-
Examples thereof include phenylstyryltriphenylamine compounds, butadiene compounds, hexatriene compounds, carbazole compounds and condensed polycyclic compounds. Specific examples of this carrier transporting material include, for example, JP-A-61-107356.
The carrier transporting substances described in No.
The structures of particularly representative ones are shown in "Chemical formula 17" to "Chemical formula 22" below.

[0071]

[Chemical 17]

[0072]

[Chemical 18]

[0073]

[Chemical 19]

[0074]

Embedded image

[0075]

[Chemical 21]

[0076]

[Chemical formula 22]

The carrier generation layer is made of a carrier generation material (CG
M) It can be formed by itself or by adding a suitable binder resin thereto, or by further adding a substance having a high mobility for carriers of a specific or non-specific polarity (that is, a carrier transporting substance). .

As a specific forming method, C is formed on the support.
Examples thereof include a method in which GM is vacuum-deposited, and a method in which CGM is dissolved or dispersed in an appropriate solvent alone or together with an appropriate binder resin, and then applied (or dip coated) and dried.

In this latter method, a binder resin or a carrier-transporting substance may be added, in which case the ratio of carrier-generating substance: binder resin: carrier-transporting substance is 1: (0-100) :( 0-500), particularly 1: (0-10) :( 0-50).

For each of the constituent layers of the carrier transport layer, a solvent or a dispersion in which a carrier transport substance and a binder resin are dissolved and dispersed in a solvent is applied onto the carrier generation layer or another constituent layer of the carrier transport layer. It can be dried and formed.

It is also possible to prevent the binder resin for coating and forming the lower constituent layer 3A from being so much soluble (low solubility) in the solvent for coating and forming the upper constituent layer 3B. In this case, diffusion of the carrier transport substance or isocyanate into the lower constituent layer 3A, the lower constituent layer 3A
Can be prevented from swelling.

Each layer of the photoreceptor is dip coated, spray coated,
It can be formed by various coating methods such as blade coating, roll coating, spiral coating and slide hopper coating.

Further, the coating method of forming the upper constituent layer 3B and the lower constituent layer 3A can be different. For example, if the constituent layer 3A is formed by dip coating and the constituent layer 3B is formed by spray coating, dissolution and swelling of the lower constituent layer 3A can be prevented.

Conventionally, when an organic photoconductive photoreceptor is applied and formed, various application methods such as dip application, blade application, spin application, beam application and spiral application have been used, but the application method is easy. Further, 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, when the lower layer is dissolved during the application of the surface layer, the coating film is destroyed, 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,
Image unevenness partially or locally differs in electrophotographic performance, image quality is degraded, and photoelectric and functional durability are also degraded, resulting in impaired electrophotographic performance. Further, in the dip coating method, the objects to be coated are dipped one by one in a tank containing a large amount of the coating liquid for coating, so that the coating liquid is wasted and the coating efficiency is poor. The coating solution in the inside may change to cause variations in electrophotographic performance. In particular, when a crosslinking agent such as isocyanate is added as in the present invention, the change with time of the coating solution is severe.

Therefore, the above problem can be solved by using a circular amount regulating type coating machine (for example, a circular slide hopper coating machine) for at least the constituent layer on the surface region side as in the present invention. Further, in the present invention, at least the above Even if different carrier transporting substances are used in the constituent layer on the surface region side and other constituent layers, against the problem that unnecessary mixing occurs due to elution of the lower layer carrier transporting substance to the coating liquid for the constituent layer on the surface region side However, it is an effective means.

The coating principle and characteristics of the circular amount regulation type coating machine are disclosed in JP-A-60-95440 and Japanese Patent Application No. 3-90250.

The coating by the coating device of the present invention is performed as follows. That is, in a coating device that applies a coating liquid while moving a base material having a continuous peripheral surface formed endlessly, the coating liquid can continuously contact the base material so as to surround the peripheral surface of the base material. A hopper coating surface is formed so as to maintain a gap, and a coating liquid distribution chamber that directly supplies the coating liquid to the hopper coating surface through a coating liquid distribution slit is provided so as to surround the peripheral surface of the base material, and A coating liquid supply port for continuously supplying the coating liquid to the coating liquid distribution chamber is provided, and a coating liquid discharge port for discharging the coating liquid to the outside of the coating liquid distribution chamber is provided in the coating device. The coating liquid sent by a pump or the like into the liquid distribution chamber is supplied from the coating liquid supply port, the coating liquid from the supply port is distributed in the circumferential direction of the base material, and flows so as to surround the substrate. Through the distribution slit, To a outlet effluent from the coating liquid flow outlet. The coating liquid extruded from the outflow port flows out into the gap and is coated at the liquid contact portion on the peripheral surface of the base material.

The coating liquid supply device according to the present invention can be suitably used not only for a single layer coating device but also for a weight coating device for simultaneously coating two or more coating liquids.

The protective layer, the intermediate layer or the undercoat layer can be formed by applying a solution prepared by dissolving a binder resin in a solvent and drying it.

A wide variety of solvents or dispersion media can be used as the solvent or dispersion medium for forming the photosensitive layer. For example, n-butylamine, ethylenediamine, N, N-dimethylformamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 4-methoxy-4-methyl-2-pentanone, tetrahydrofuran, dioxane, ethyl acetate, acetic acid n -Butyl, t-butyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, toluene, xylene, acetophenone, methanol, ethanol, propanol, butanol, cyclolomethane, 1,2-dichloroethane, trichloroethane, chloroform and the like. .

The photosensitive layer may contain an electron-accepting substance for the purpose of improving sensitivity, reducing residual potential, or reducing fatigue during repeated use. Examples of such an electron accepting substance include succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride and 4-nitroanhydride. Phthalic acid, pyromellitic dianhydride, mellitic dianhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride , Quinone chlorimide, chloranil, bromanil, dichlorodiciaci-p-benzoquinone, anthraquinone, dinitroanthraquinone, 9-fluorenylidene malononitrile, polynitro-9-fluorenylidene malononitrile, picric acid, o-nitrobenzoic acid, p-nitro Benzoic acid, 3,5-dinitrobenzoic acid, pentafluoro Ikikosan, 5-nitro salicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, mellitic acid, and larger compounds of other electronic Shinwa force.

The addition ratio of the electron accepting substance is preferably 0.01 to 200 with respect to 100 by weight of the carrier generating substance, and further,
0.1-100 is preferable.

Further, in the above-mentioned photosensitive layer, storage stability, durability,
For the purpose of improving the resistance to the environment, a deterioration inhibitor such as an antioxidant or a light stabilizer can be contained. Examples of compounds used for such purpose include chromanol derivatives such as tocopherol and its etherified or esterified compounds, polyarylalkane compounds,
Hydroquinone derivatives and mono- and dietherified compounds thereof, benzophenone derivatives, benzotriazole derivatives, thioether compounds, phosphonic acid esters, phosphorous acid esters, phenylenediamine derivatives, phenol compounds, hindered phenol compounds, linear amine compounds, cyclic amine compounds, Hindered amine compounds are effective. Specific examples of particularly effective compounds include "IRGA
"NOX 1010", "IRGANOX 565" (manufactured by Ciba-Geigy), "Sumilyzer BHT", "Sumilyzer MD"
P ”(Sumitomo Chemical Co., Ltd.) and other hindered phenolic compounds“ Sanol LS-2626 ”,“ Sanol LS-622 ”
LD ”(manufactured by Sankyosha Co., Ltd.) and the like.

As the binder used in the intermediate layer, the protective layer and the like, those mentioned above for the carrier generating layer and the carrier transporting layer can be used. In addition to them, nylon resin, ethylene-vinyl acetate copolymer, Ethylene resins such as ethylene-vinyl acetate-maleic anhydride copolymer and ethylene-vinyl acetate-methacrylic acid copolymer, polyvinyl alcohol, and cellulose derivatives are effective. Further, a curable binder that uses heat curing or chemical curing such as melamine, epoxy, or isocyanate can be used.

As the conductive support, a metal plate or a metal drum may be used, and a conductive polymer, a conductive compound such as indium oxide, or a thin layer of a metal such as aluminum or palladium may be applied, vapor deposited, laminated or the like. Therefore, the one provided on a substrate such as paper or plastic film can be used.

The photoconductor of the present invention can be used in electrophotographic copying machines, laser beam printers, CRT printers, electrophotographic plate making systems and the like. At that time, as a light source, He-N
e laser, semiconductor laser (780 nm, 680 nm, etc.), LED,
Various light sources such as halogen lamps can be used.

[0097]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. In the text, "part" means "part by weight".

Example 1 An undercoat layer made of polyamide resin and having a thickness of about 0.1 μm was provided on a drum-shaped aluminum conductive support (aluminum cylinder) having a diameter of 80 mm. Then CGM-1 30
Part, butyral resin B (BX-L (manufactured by Sekisui Chemical Co., Ltd.)) 10
And 1600 parts of methyl ethyl ketone were applied onto the above-mentioned undercoat layer by dip coating so that the film thickness after drying was 1.5 μm to form a carrier generation layer.

Then, the carrier transport material CTM-1 500
Part, polycarbonate resin (Z300 manufactured by Mitsubishi Gas Chemical Co., Inc.) 5
A mixture of 60 parts, 140 parts of bisphenol Z-type polycarbonate diol (average molecular weight 2500), and 14 parts of diphenylmethane diisocyanate "Compound Example (7)"
A liquid dissolved in 3600 parts of 2-dichloroethane was applied by dip coating so that the film thickness after drying was 30 μm, to form a carrier transport layer. This carrier transport layer is 2 at 120 ℃
Allowed to cure for hours.

[0100]

[Chemical formula 23]

Example 2 A photoconductor was prepared in the same manner as in Example 1 except that 340 parts of polycarbonate diol was used.

Example 3 A photoconductor was prepared in the same manner as in Example 1 except that 3 parts of polycarbonate diol was used in Example 1.

Example 4 Photosensitization was carried out in the same manner as in Example 1 except that Y-type titanyl phthalocyanine having a clear peak mainly at 27.2 ° of Bragg angle 2θ was used in place of CGM-1 as the carrier generating material in Example 1. The body was made.

Example 5 A photoconductor was prepared in the same manner as in Example 1 except that the silane compound (27) was used instead of using diphenylmethane diisocyanate in Example 1.

Example 6 A photoconductor was prepared in the same manner as in Example 1 except that a silane crosslinking agent (11) was used instead of using diphenylmethane diisocyanate in Example 1.

Example 7 In the same manner as in Example 1 except that 1 part of a phenol-modified polysiloxane (X-22-165B manufactured by Shin-Etsu Chemical Co., Ltd.) of the following "Chemical Formula 24" was added to the carrier transport layer in Example 1. A photoconductor was prepared.

[0107]

[Chemical formula 24]

Example 8 A photoconductor was prepared in the same manner as in Example 1 except that 1 part of carbinol-modified polysiloxane (X-22-160AS manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the carrier transport layer. .

Example 9 A photoreceptor was prepared in the same manner as in Example 8 except that melamine resin (Uban 21R, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used in place of diphenylmethane diisocyanate in Example 8.

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that diphenylmethane diisocyanate was not used.

Example 10 An undercoat layer made of polyamide resin and having a thickness of about 0.1 μm was provided on a drum-shaped aluminum conductive support (aluminum cylinder) having a diameter of 80 mm. Then CGM-1 30
Part of butyral resin B (BX-L) 10 was applied so that the film thickness after drying would be 1.5 μm to form a carrier generation layer.

Then, the carrier transport material CTM-2 500
Part, polycarbonate resin (Z300 manufactured by Mitsubishi Gas Chemical Co., Inc.) 5
A solution prepared by dissolving 60 parts in 3600 parts of dichloromethane was applied by dip coating so that the film thickness after drying was 30 μm, and a carrier transport layer was formed as a support-side constituent layer.

[0113]

[Chemical 25]

Further, 250 parts of carrier transport material CTM-2,
Polycarbonate resin (Z300 manufactured by Mitsubishi Gas Chemical Co., Inc.) 280
Part, 70 parts of bisphenol Z-type polycarbonate diol (average molecular weight 2500), and 7 parts of diphenylmethane diisocyanate are dissolved in 5000 parts of 1,2-dichloromethane to form a film having a thickness of 5 μm after drying.
Was applied to form a carrier transport layer on the surface region side. The carrier transport layer was cured at 120 ° C for 2 hours.

Example 11 A photoconductor was prepared in the same manner as in Example 10 except that 170 parts of polycarbonate diol was used in Example 1.

Example 12 A photoconductor was prepared in the same manner as in Example 11 except that 1.5 parts of polycarbonate diol was used in Example 1.

Example 13 A photoconductor was prepared in the same manner as in Example 10 except that the silane compound (27) was used in place of the diphenylmethane diisocyanate in the coating liquid for forming the carrier transport layer on the surface region side. did.

Example 14 Example 10 was repeated except that the silane coupling agent (11) was used in place of diphenylmethane diisocyanate in the coating liquid for forming the carrier transport layer on the surface region side in Example 10.
A photoconductor was prepared in the same manner as in.

Example 15 A photoreceptor was prepared in the same manner as in Example 10 except that 1 part of phenol-modified polysiloxane (X-22-165B manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the carrier transport layer on the surface region side. It was made.

Example 16 A photoreceptor was prepared in the same manner as in Example 10, except that 1 part of carbinol-modified polysiloxane (X-22-160AS manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the carrier transport layer on the surface region side. Was produced.

Example 17 A photoconductor was prepared in the same manner as in Example 15 except that melamine resin (Uban 21R, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used instead of using diphenylmethane diisocyanate in Example 15.

Comparative Example 2 A photoconductor was prepared in the same manner as in Example 1 except that diphenylmethane diisocyanate was not used in Example 10.

<Evaluation of Electrophotographic Photosensitive Member> The electrophotographic photosensitive member obtained as described above was used as a copying machine Konica U manufactured by Konica Corporation.
-The following characteristics were evaluated using BIX4045. The results are shown in Tables 1 and 2.

[0124]

[Table 1]

[0125]

[Table 2]

1. Evaluation of electrical and repetitive characteristics Charging by modifying the above copying machine and installing a surface electrometer
The black paper potential, the white paper potential, and the residual potential (Vb, Vw, and Vr) at the first time and the 50,000th time when the process of exposure → charge removal was repeated 50,000 times were measured and evaluated. The black paper potential here means the surface potential of the photoconductor when a black paper original having a reflection density of 1.3 is copied. Similarly, the blank sheet potential means the surface potential of the photoconductor when copying a blank sheet document having a reflection density of 0.0.

2. Image evaluation Image samples after copying 50,000 sheets showed background defects, white lines and black lines in halftone images, and image defects due to photoconductor deterioration (thickness loss, electrical characteristics) such as uneven density. I searched for it.

3. Abrasion resistance evaluation The abrasion resistance of the photoconductor was evaluated by the change amount of the photoconductor film thickness before and after the actual copying test of 50,000 copies. The thickness of the photoconductor is
It was measured with EDDY560C manufactured by Fischer.

[0129]

According to the present invention, it is possible to provide a highly durable photoreceptor having high mechanical strength and excellent charging potential, sensitivity and residual potential characteristics.

[Brief description of drawings]

FIG. 1 is a layer configuration diagram of a photoconductor used in the present invention.

[Explanation of symbols]

 1 Conductive Support 2 Carrier Generation Layer 3 Carrier Transport Layer 3A Lower Composition Layer 3B Upper Composition Layer 5 Surface (Protection) Layer 6 Intermediate Layer (Undercoat Layer)

Claims (16)

[Claims] 1. A photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a polycarbonate polymer or a copolymer thereof as a binder resin, and 1 to 50% by weight of the polymer. An electrophotographic photoreceptor containing the above polycarbonate diol, which is crosslinked by a crosslinking agent. 2. The electrophotographic photosensitive member according to claim 1, wherein the crosslinking agent is an isocyanate. 3. The electrophotographic photosensitive member according to claim 1, wherein the crosslinking agent is a polyfunctional silane coupling agent. 4. The electrophotographic photosensitive member according to claim 3, wherein the silane coupling agent has a fluorinated alkyl group. 5. The electrophotographic photosensitive member according to claim 1, wherein one of the constituents of the photosensitive layer is a siloxane polymer having a hydroxyl group at the terminal. 6. The electrophotographic photoreceptor according to claim 5, wherein the siloxane polymer is crosslinked with a polycarbonate diol by a crosslinking agent. 7. The electrophotographic photosensitive member according to claim 6, wherein the crosslinking agent is an isocyanate. 8. A photoreceptor comprising a photosensitive layer having a carrier generation layer and a carrier transport layer laminated on at least a conductive support, wherein the carrier transport layer comprises a plurality of constituent layers, At least the outermost layer thereof contains a polycarbonate polymer or a copolymer thereof as a binder resin, and contains 1 to 50% by weight of the polymer of a polycarbonate diol, and the diol is crosslinked by a crosslinking agent. An electrophotographic photosensitive member characterized in that 9. The electrophotographic photosensitive member according to claim 8, wherein the crosslinking agent is an isocyanate. 10. The electrophotographic photosensitive member according to claim 8, wherein the crosslinking agent is a polyfunctional silane coupling agent. 11. The electrophotographic photosensitive member according to claim 8, wherein the cross-linking agent is a silane coupling agent, and the silane coupling agent has a fluorinated alkyl group. 12. The electrophotographic photosensitive member according to claim 8, wherein one of the constituent raw materials of the photosensitive layer is a siloxane polymer having a hydroxyl group at a terminal. 13. The electrophotographic photosensitive member according to claim 12, wherein the siloxane polymer is crosslinked with a polycarbonate diol by a crosslinking agent. 14. The electrophotographic photosensitive member according to claim 12, wherein the crosslinking agent is an isocyanate. 15. A method for producing a photosensitive member comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a polycarbonate polymer or a copolymer thereof as a binder resin, and A method for producing an electrophotographic photosensitive member, which comprises 50% by weight of a polycarbonate diol, and the diol is contained after being crosslinked with a crosslinking agent. 16. A photoconductor comprising a photosensitive layer having a carrier generation layer and a carrier transport layer laminated on at least a conductive support, wherein the carrier transport layer comprises a plurality of constituent layers, At least the outermost layer contains a polycarbonate polymer or a copolymer thereof as a binder resin, and contains 1 to 50% by weight of the polymer of a polycarbonate diol, and the diol is contained by being crosslinked with a crosslinking agent. And a method for manufacturing an electrophotographic photosensitive member.