JPH0683081A - Laminar photosensitive body - Google Patents

Abstract

PURPOSE:To improve the coating property, cleaning property, wear resistance and durability, to lessen fatigue for repetition of use, and to enhance sensitivity by using a charge transfer layer combined with a specified binder resin and a charge transfer material. CONSTITUTION:This charge transfer layer contains at least one kind of amino compd. expressed by formula I and at least one kind of polycarbonate resin expressed by formula II as the binder resin. In the formula I, Ar1-Ar4 are alkyl groups, aralkyl groups, etc., R1-R3 are hydrogen atoms, alkyl groups, or alkoxy groups, and X is -O-, -S-, etc. In the formula II, R7-R10 and R13-R16 are hydrogen atoms, alkyl groups, aryl groups or halogen atoms, R11 and R12 are hydrogen atoms, alkyl groups such as methyl, ethyl, propyl, butyl and pentyl groups, cyclic alkyl groups such as cyclohexyl groups, norbornan ring, etc., or aryl groups such as phenyl and naphthyl groups, m is 0-500, and n is 5-100.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated type photoreceptor having a charge generating layer and a charge transporting layer on a conductive support, and more specifically, a charge transporting material used for forming the charge transporting layer. The present invention relates to a combination of binder resins for binding it.

[0002]

2. Description of the Related Art Conventionally, as a photoreceptor, one having a photosensitive layer containing an inorganic photoconductive material as a main component and one having a photosensitive layer containing an organic photoconductive substance as a main component are known. Inorganic materials have drawbacks such as high toxicity, poor film-forming property, lack of flexibility, and high manufacturing cost.

On the other hand, research using organic photoconductive substances represented by polyvinylcarbazole compounds in the photosensitive layer of the photoconductor has progressed and has already been put to practical use. In general, an organic photoconductive substance is better in transparency, lighter in weight and excellent in film forming property than an inorganic photoconductive substance, but inferior in terms of sensitivity, durability and stability due to environmental changes. Therefore, the charge generation function and the charge transport function in the photoconductive function are separately assigned to different substances, and high sensitivity and repetitive stability,
A function-separated photoreceptor having excellent durability has been developed. The above-mentioned function-separated type photoreceptor has a photosensitive layer in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated, or a charge generation material and a charge transport material. Some have a photosensitive layer contained in a binder resin.

However, even in the above-mentioned function-separated type laminated photoconductor, unevenness in the film thickness of the photoconductor, poor cleaning of the photoconductor surface, deterioration due to humidity and ozone, and the like cause uneven density in the image. When 100 sheets are continuously copied, there are problems such as shading of the image and blurring of the image.

In particular, when used as a photoconductor of a laser printer or the like which is required to have high image quality reliability and repeated stability, such a problem becomes serious, and a photoconductor which can be suitably used in a laser printer or the like is required. Came to be.

The above-mentioned problems are largely due to the coating state of the photosensitive layer, particularly the charge transport layer, such as coating accuracy and scratches, abrasion and deterioration due to mechanical and physical external forces during printing. This largely depends on the characteristics of the binder resin used for forming the photosensitive layer.

Therefore, in order to solve such a problem,
Various binder resins including polycarbonate have been investigated.

However, when a charge transporting material having a poor matching with the binder resin is used, the coating solution of the composition has poor coatability, so-called "repellency" is apt to occur in the photosensitive layer, and white spots occur in the copied image. ("Hajiki" means when the photosensitive layer is applied,
It means the phenomenon that a crater-like recess is created on the coated surface.) Further, the coating solution has poor coating storability, and even if the coating solution is uniformly mixed and dissolved after the preparation, it will be repelled again when stored for a long time.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and by using a charge-transporting layer in which a specific binder resin and a specific charge-transporting material are combined, coating property and cleaning property can be obtained. It is an object of the present invention to provide a high-sensitivity photoconductor having excellent wear resistance and durability, little fatigue against repeated use, and stable electrophotographic characteristics.

[0010]

That is, according to the present invention, in a laminated type photoreceptor having a charge generation layer and a charge transport layer provided on a conductive support, the charge transport layer is represented by the following general formula [I]:

[Chemical 4] The following general formula [II] is used as the binder resin and at least one amino compound represented by:

[Chemical 5] The present invention relates to a laminated type photoreceptor containing at least one polycarbonate resin represented by By using the amino compound represented by the general formula [I] as a charge transport agent and the polycarbonate resin represented by the general formula [II] as a binder resin in combination, the coating property, the cleaning property and the resistance to It is possible to provide a high-sensitivity photoreceptor having excellent wear resistance and durability, little fatigue against repeated use, and stable electrophotographic characteristics.

In the general formula [I], Ar ₁ , Ar ₂ , Ar ₃ and A
r ₄ are each independently an alkyl group such as methyl,
It represents an ethyl or propyl group, an aralkyl group such as a benzyl group or a phenethyl group, an aryl group such as a phenyl group or a naphthyl group, a biphenyl group or a heterocyclic group such as a thienyl, furyl, bithienyl or dioxaindane residue. These groups include substituents such as alkyl groups (methyl, ethyl, propyl, etc.), halogen atoms (chlorine atom, hydrogen atom, etc.), alkoxy groups (methoxy, ethoxy, phenoxy, etc.), aryl groups (phenyl group, etc.). It may have an aralkyl group (benzyl etc.) or a heterocycle (thiophene etc.).

R ₁ , R ₂ and R ₃ are each independently
It represents a hydrogen atom, an alkyl group such as methyl, ethyl or propyl, an alkoxy group such as methoxy or ethoxy, or a halogen atom such as chlorine or silicon.

X is

[Chemical 6] Represents

In the above formula, R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group such as methyl, ethyl, propyl or butyl, an aralkyl group such as benzyl or phenethyl, an aryl group such as Phenyl or naphthyl or the like or a heterocyclic group such as thienyl or furyl or the like is shown. These groups have a substituent, for example, an alkyl group (methyl, ethyl, propyl, etc.), a halogen atom (chlorine atom, arsenic atom, etc.), an aryl group (phenyl group, etc.) or an aralkyl group (benzyl, etc.). May be. Indicates.

The charge transport material used in the charge transport layer of the photoconductor of the present invention contains at least one amino compound represented by the above general formula [I].

The amino compounds represented by the above formula [I] are all asymmetrical with respect to X and have poor crystallinity, and show good compatibility with the binder resin. In terms of sensitivity, at least one of Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ is used.
It is desirable that one can be a biphenyl group.

The amino compound represented by the general formula [I] of the present invention can be synthesized, for example, by the following method.

For example, the following general formula [III]:

[Chemical 7]

[Wherein R ₁ , R ₂ , R ₃ and X are general formulas
An iodo compound represented by the same meaning as that of [I], and the following general formulas [IV] and [V]:

[Chemical 8] [Wherein Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ have the same meanings as those in the general formula [I]], in the presence of a basic compound, a transition metal or a transition metal compound catalyst, and a solvent. It can be synthesized by the Ullmann reaction.

The reaction is generally 100 to 250 ° C. under normal pressure.
However, it may be carried out under pressure. After the reaction is completed, the solid matter precipitated in the reaction solution is removed and then the solvent is removed to obtain the product.

As the basic compound used in the present invention, alkali metal hydroxides, carbonates, hydrogen carbonates, alcoholates and the like are generally used, and quaternary ammonium compounds, aliphatic amines and aromatic compounds are used. It is also possible to use organic bases such as amines. Of these, alkali metal and quaternary ammonium carbonates and hydrogen carbonates are preferable. From the viewpoint of reaction rate and thermal stability, alkali metal carbonates and hydrogen carbonates are most preferable.

Examples of the transition metal or transition metal compound used in the synthesis of the amino compound of the present invention include Cu,
Metals such as Fe, Co, Ni, Cr, V, Pd, Pt and Ag and their compounds are used, but copper and palladium and their compounds are preferable from the viewpoint of yield. The copper compound is not particularly limited, and most copper compounds are used, but cuprous iodide, cuprous chloride, cuprous oxide, cuprous bromide, cuprous cyanide, cuprous sulfate. , Cupric sulfate, cupric chloride, cupric hydroxide, cupric oxide, cupric bromide, cupric phosphate, cuprous nitrate, cupric nitrate, copper carbonate, acetic acid first Copper, cupric acetate, etc. are preferred. Among them, especially CuC
l, CuCl ₂ , CuBr, CuBr ₂ , CuI, CuO, Cu
₂ O, CuSO ₄ , and Cu (OCOCH ₃ ) ₂ are preferable because they are easily available. As the palladium compound, halides, sulfates, nitrates, organic acid salts and the like can be used. The amount of the transition metal and its compound used is preferably 0.5 to 500 mol% of the halogenated diphenyl derivative to be reacted.

The solvent used in the synthesis may be a commonly used solvent, but an aprotic polar solvent such as nitrobenzene, dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone is preferable.

The general formulas used in the photoreceptor of the present invention are shown below.
Specific examples of the amino compound represented by [I] are shown below, but the invention is not limited thereto.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

[Chemical 14]

[0031]

[Chemical 15]

[0032]

[Chemical 16]

[0033]

[Chemical 17]

[0034]

[Chemical 18]

[0035]

[Chemical 19]

[0036]

[Chemical 20]

[0037]

[Chemical 21]

[0038]

[Chemical formula 22]

[0039]

[Chemical formula 23]

[0040]

[Chemical formula 24]

[0041]

[Chemical 25]

[0042]

[Chemical formula 26]

[0043]

[Chemical 27]

[0044]

[Chemical 28]

In the general formula [II], R ₇ , R ₈ , R ₉ , R ₁₀ ,
R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, an alkyl group (methyl, ethyl or propyl etc.), an aryl group (phenyl or naphthyl etc.) or a halogen atom (chlorine or bromine etc.). Represent;

R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group such as methyl, ethyl, propyl,
Examples thereof include butyl and pentyl and the like, cyclic alkyl groups such as cyclohexyl group and norbornane ring, and aryl groups such as phenyl and naphthyl. R ₁₁ and R ₁₂
Is a ring together with the carbon atom to which they are attached,
For example, a cyclohexane ring, a norbornane ring, a fluorene ring or the like may be formed.

M is a number from 0 to 500, and n is a number from 5 to 100. The number average molecular weight is preferably 20,000 to 80,000. Also,
The ratio of m to n is 9: 1 to 1: 9, preferably 9: 1 to
It is 1: 1. When n is large, hardness increases, printing durability is improved, and gelation becomes difficult. When n is small, the crystallinity is good and gelation is likely to occur.

R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R
₂₃ and R ₂₄ each independently represent a hydrogen atom, an alkyl group such as methyl, ethyl or propyl, an aryl group such as phenyl or naphthyl, or a halogen atom such as an arsenic atom or a chlorine atom.

In the present invention, from the viewpoint of durability and coatability, 1 × 10 ⁴ to 1 × 10 ⁵ , preferably 2 × 1.
A polycarbonate resin having a number average molecular weight of 0 ⁴ to 8 × 10 ⁴ is used, and more preferably, a polycarbonate resin having a number average molecular weight of 2 to 4 × 10 ⁴ and ^{4 to} 6.5 × 10 ⁴ is mixed and used. . Number average molecular weight is 1 x 10
^{If it is} less than ⁴ , the hardness of the film becomes soft and the durability deteriorates. On the other hand, if the number average molecular weight is larger than 1 × 10 ⁵ , the viscosity will be high and the coatability will be poor, making it difficult to apply it uniformly.
The polycarbonate resin represented by the general formula [II] used as the binder resin in the charge transport layer of the photoreceptor of the present invention can be prepared by using the diol compound represented by the following general formulas [VI] and [VII] by the phosgene method. It can be synthesized by copolymerization by a general polycarbonate synthesis method such as.

[0050]

[Chemical 29]

[Chemical 30] [In the formula, R _{7 to} R ₂₄ have the same meaning as in the general formula [II]]

The general formula [I] used in the photoreceptor of the present invention is
Specific examples of the polycarbonate resin represented by I] include, but are not limited to, those shown below.

[0052]

[Chemical 31]

[0053]

[Chemical 32]

[0054]

[Chemical 33]

[0055]

[Chemical 34]

The layered type photoconductor in which the charge generation layer and the charge transport layer are laminated on the conductive support is specifically described below.

The laminated photoreceptor of the present invention is produced by vacuum-depositing a charge generating material on a conductive support, or by dispersing it in an appropriate solvent or a solution in which a binder resin is dissolved if necessary. The applied coating solution is applied and dried to form a charge generation layer. At this time, the thickness of the charge generation layer is 0.01 to 2 μm.
m, preferably 0.1 to 1 μm. If the amount of the charge generating material used is too small, the sensitivity is poor, and if it is too large, the charging property becomes poor or the mechanical strength becomes weak. The amount is 0 to 10 parts by weight, preferably 0 to 5 parts by weight, relative to 1 part by weight of the generating material. Examples of the charge generation material include bisazo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes, azo dyes, quiadrin dyes, indigo dyes. , Perylene dyes, polycyclic quinone pigments, bisbenzimidazole pigments, induslon pigments, squarylium pigments, phthalocyanine pigments, pyrrolopyrrole pigments, and other organic substances, and selenium, selenium tellurium, selenium arsenic, sulfide. Inorganic substances such as cadmium and amorphous silicon can be used. In addition, any material can be used as long as it absorbs light and generates charge carriers with an extremely high probability.

When the charge generating layer is formed by using the binder resin, it is electrically insulative, and it is measured by itself and is 1 × 10 ¹² Ω.
-It is desirable to have a volume resistance of cm or more. For example,
Known binders such as thermoplastic resins, thermosetting resins, photocurable resins, and photoconductive resins can be used. Specifically, saturated polyester resin, polyamide resin, acrylic resin, ethylene-vinyl acetate resin, ion-crosslinked olefin copolymer (ionomer), styrene-butadiene block copolymer, polycarbonate, vinyl chloride-vinyl acetate copolymer, Thermoplastic resin such as cellulose ester, polyimide, styrene resin: epoxy resin, urethane resin, silicone resin, phenol resin,
Thermosetting resins such as melamine resins, xylene resins, alkyd resins, and thermosetting acrylic resins; photocurable resins; photoconductive resins such as polyvinylcarbazole, polyvinylpyrene, polyvinylanthracene, and polyvinylpyrrole, and the like. The resin to be used is used alone or in combination of two or more kinds.

The solvent for dissolving these resins varies depending on the kind of the resin. For example, alcohols such as methanol, ethanol and iso-propyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexane, N, N-dimethylformaldehyde. , Amides such as N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, tetrahydrofuran, dioxane,
Ethers such as ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, dichloroethylene, carbon tetrachloride,
Aliphatic halogenated hydrocarbons such as trichlorethylene,
Or benzene, toluene, xylene, ligroin,
Aromatic compounds such as monochlorobenzene and dichlorobenzene can be used.

Further, together with the binder resin, a plasticizer such as halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutyl phthalate, o-terphenyl, chloranil, tetracyanoethylene, 2,4,7-trinitrofluorenone, 5 , 6-dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride,
An electron-withdrawing sensitizer such as 3,5-dinitrobenzoic acid and a sensitizer such as methyl violet, rhodamine B, cyanine dye, pyrylium salt and thiapyrylium salt may be used.

In the photoreceptor of the present invention, an amino compound represented by the general formula [I] is used as a charge transport material and a polycarbonate resin represented by the general formula [II] is used as a binder resin on a charge generation layer in a suitable solvent. The solution dissolved in is applied and dried to form a charge transport layer. At this time, the thickness of the charge transport layer is 3 to 40 μm, preferably 5 to 30 μm.

The ratio of the amino compound in the charge transport layer is 0.02 to 2 parts by weight, preferably 0.03 to 1.2 parts by weight, based on 1 part by weight of the binder resin. If the amount is less than 0.02 parts by weight, the sensitivity is deteriorated and the residual potential during printing is increased. If the amount is more than 2 parts by weight, deterioration due to printing durability is large and the dark decay speed is increased.

As the solvent for dissolving the polycarbonate resin represented by the general formula [II], the above ether solvent,
Halogenated hydrocarbons, aromatics and the like can be used.

The polycarbonate resin may be used in combination with other resins. In that case, the proportion of the polycarbonate resin in the charge transport layer is 50% by weight or more. When the content of the polycarbonate resin is less than 50% by weight based on the total weight of the resin in the charge transport layer, the hardness of the film itself is lowered, the durability is deteriorated, and the sensitivity is lowered. Examples of the resin that can be used in combination with the polycarbonate resin include polystyrene resin, polymethylmethacrylate resin, polyester resin, polyacrylate resin, and phenoxy resin.

The charge transport layer may further contain known antioxidants, sensitizers, thickeners, surfactants, anti-curl agents, ultraviolet absorbers, plasticizers, leveling agents and the like. .

The photoconductor of the present invention may have a constitution in which an intermediate layer is provided on a conductive support, whereby the adhesion is improved, the coatability is improved, the support is protected, and the support side. From the above, it is possible to improve the charge injection property to the photosensitive layer.

Suitable materials for the intermediate layer are polyimide, polyamide, nitrocellulose, polyvinyl butyral, polyvinyl alcohol, aluminum oxide and the like, and the film thickness is preferably 1 μm or less.

Further, the photoreceptor of the present invention may be provided with a surface protective layer. As a material used for the surface protective layer, a polymer such as an acrylic resin, a polyaryl resin, a polycarbonate resin, or a urethane resin is directly used,
Alternatively, a material in which a low resistance compound such as tin oxide or indium oxide is dispersed is suitable.

It is also possible to use organic plasma polymerized membranes. The organic plasma polymerized film is appropriately oxygen,
It may contain nitrogen, halogen, Group III or Group V atom of the periodic table. The thickness of the surface protective layer is preferably 5 μm or less.

In the laminated type photoreceptor of the present invention,
A charge transport layer and a charge generation layer on a conductive support may be laminated in this order.

As the conductive support used in the photoreceptor of the present invention, a sheet or drum of foil or plate of copper, aluminum, iron, nickel or the like is used. Further, these metals are attached to a plastic film or the like by vacuum vapor deposition, electroless plating or the like, or a layer of a conductive compound such as a conductive polymer, indium oxide or tin oxide is similarly formed on a paper or a plastic film. It is possible to use those provided on the support by coating or vapor deposition.

The present invention will be described below with reference to examples.

[0073]

[Synthesis Example] The method for synthesizing the amino compound represented by the amino compound example [2] is shown below. 4-iododiphenyl-4'-p-iodobenzyl 50 g (0.10 mol), 3-
44 g (0.24 mol) of methyldiphenylamine, 35 g (0.3 mol) of potassium carbonate, 10 g (0.16 mol) of copper powder and 400 g of nitrobenzene were charged into a 4-liter flask equipped with a reflux condenser and charged with nitrogen. 1 at 200 ° C under air flow
The reaction was stirred for 8 hours. After the reaction was completed, 200 g of tetrahydrofuran was added to the reaction solution, and then the solid matter was filtered.
After the filtrate was separated by silica gel column chromatography, the separated product was recrystallized in a toluene-ethanol mixed solvent for purification to obtain white crystals having a melting point of 75 to 76 ° C.

The results of elemental analysis are as follows ((C ₄₅
H ₃₈ N ₂ )).

[0075]

[Table 1]

[0076]

EXAMPLES The amino compounds of the present invention used in the following examples were synthesized by the above-mentioned synthesis examples or a method similar thereto.

Example 1 The following chemical formula:

[Chemical 35] 0.45 part by weight of the bisazo compound represented by, 0.45 part by weight of a polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) and 50 parts by weight of cyclohexanone were dispersed using a sand mill. The resulting dispersion of the bisazo compound was applied on a 100 μm thick aluminized mylar using a film applicator to a dry film thickness of 0.3 g / m ^2, and then dried to form a charge generation layer. did.

An amino compound [3] 5 is formed on the charge generation layer.
0 parts by weight and 70 parts by weight of the polycarbonate resin represented by the chemical formula (II-1) (m and n are about 100)
A solution prepared by dissolving 400 parts by weight of dioxane and 100 parts by weight of cyclohexanone was applied to a dry film thickness of 20 μm and dried to form a charge transport layer. In this way, a laminated type photoreceptor having a two-layered photosensitive layer was produced.

The photoreceptor prepared as described above was incorporated into a commercially available electrophotographic copying machine (EP-470Z manufactured by Minolta Camera Co., Ltd.) and charged by corona discharge of -6 kV to obtain an initial surface potential V ₀ (v) and a surface potential. There exposure required for decay to half the initial surface potential (hereinafter, half decay _{exposure) E 1/2 (Lux ·} s
ec) Attenuation rate DD of initial potential when left for 1 second
R ₁ (%) was measured. The results are shown in Table 3.

Further, for the photoconductor of Example 1 and the photoconductors of Examples 2 and 28 and Comparative Examples 1, 2, 5 and 6 described later, a commercially available electrophotographic copying machine (manufactured by Minolta Camera Co .; E
P-5400) and repeated real-time photographing at the time of negative charging. V _0, E _1/2 in 10000 Stock longitudinal for each photoreceptor was measured residual potential V _R (v) and the film thickness. In addition, the image characteristics after 10,000 actual copies were also evaluated. The results are shown in Table 5.

The image characteristic evaluations in Table 5 were ranked as follows. "Yu"; no problem compared to the early days. “Good”; somewhat inferior to the initial stage, but practically no problem. "No": The image quality is very inferior to the initial one and there is a problem.

In the photoconductors of Examples 1, 2, and 28,
It was confirmed that, as in the initial stage, the final image was excellent in gradation, there was no change in sensitivity and a clear image was obtained, and the photoreceptor of the present invention was stable in repeatability.

Examples 2 to 5 The same as Example 1 except that the amino compounds [5], [7], [10] and [11] were used in place of the amino compound [1] used in Example 1. Four types of laminated photoconductors were produced by the method.
For each of the photoconductors, V ₀ , E ₁
/ ₂ and DDR ₁ were measured and the results are shown in Table 3.

Example 6 The following chemical formula:

[Chemical 36] 0.45 part by weight of the bisazo compound represented by and 0.45 part by weight of polyvinyl butyral were dispersed by a sand mill together with 50 parts by weight of cyclohexanone. The resulting dispersion of the bisazo compound was applied on a 100 μm thick aluminized mylar using a film applicator to a dry film thickness of 0.3 g / m ^2, and then dried to form a charge generation layer. did. On this, 40 parts by weight of the amino compound [12] and 60 parts by weight of the polycarbonate resin represented by the chemical formula (II-2) (m≈100, n≈50) were added 1,4-
A solution dissolved in 500 parts by weight of dioxane was applied by dip coating so as to have a dry film thickness of 20 μm, and dried to form a charge transport layer, to prepare a photoreceptor having a photosensitive layer composed of two layers. For this photosensitive member, V
_0, E _1/2, to measure the DDR _1, and the results are shown in Table 3.

Examples 7 to 10 Similar to Example 1 except that diamino compounds [16], [17], [18] and [20] were used in place of the diamino compound [12] used in Example 6. Four types of laminated photoconductors were produced by the method. For each of the photoconductors, V in the same manner as in Example 1
_0, E _1/2, to measure the DDR _1, The results are shown in Table 3.

Example 11 1 part by weight of τ type metal-free phthalocyanine, 0.5 part by weight of polyvinyl butyral and 50 parts by weight of tetrahydrofuran (THF) were dispersed in a sand mill. The resulting phthalocyanine-based dispersion was applied on aluminized mylar having a thickness of 100 μm using a film applicator to a dry film thickness of 0.2 g / m ^2, and then dried to form a charge generation layer. did. A solution prepared by dissolving 40 parts by weight of the amino compound [25] and 60 parts by weight of the polycarbonate resin represented by the chemical formula (II-5) (m≈80, n≈20) in 500 parts by weight of dichloroethane was dried on the above. Is 25μ
Then, the charge-transporting layer was formed by coating so as to have a thickness of m, and a charge-transporting layer was formed to prepare a laminated-type photoreceptor having a photosensitive layer composed of two layers. For this photosensitive member, V ₀ ,
Measuring the E _1/2, DDR _1, and the results are shown in Table 3.

Examples 12 to 15 The same as Example 11 except that amino compounds [28], [30], [31] and [36] were used in place of the diamino compound [25] used in Example 11. Four types of laminated photoconductors were produced by the method. For each of the photosensitive member in the same manner as in Example 1 were measured _{V 0, E 1/2,} DDR 1, The results are shown in Table 3.

Example 16 0.5 parts by weight of a titanyl phthalocyanine pigment, 0.2 parts by weight of a phenoxy resin and a polyvinyl butyral resin of 0.
3 parts by weight was dispersed together with 50 parts by weight of cyclohexanone using a sand mill. The titanyl phthalocyanine pigment dispersion obtained was dried on a 100 μm thick aluminized mylar using a film applicator to give a dry film thickness of 0.2.
After coating so as to be 5 g / m ² , it was dried to form a charge generation layer. 70 parts by weight of the amino compound [38],
25 parts by weight of a polycarbonate resin (m: n = 1: 1) having a molecular weight of 24000 represented by the chemical formula (II-9) and 45 parts by weight of a polycarbonate resin (m = 0) having a molecular weight of 45000 represented by the chemical formula (II-9). And 400 parts by weight of 1,4-dioxane and 100 parts by weight of cyclohexanone are applied so as to have a dry film thickness of 20 μm and dried to form a charge transport layer, which is composed of two layers. A laminated photoreceptor having a photosensitive layer was produced. The respect to the electrophotographic photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 1. The results are shown in Table 3.

Examples 17 to 20 Similar to Example 16 except that amino compounds [39], [45], [48] and [49] were used in place of the amino compound [38] used in Example 16. Four types of laminated photoconductors were produced by the method. For each of the photoconductors, V in the same manner as in Example 1
_0, E _1/2, to measure the DDR _1, The results are shown in Table 3.

Example 21 0.5 part by weight of dibromoanthanthrone and 0.5 part by weight of polyvinyl butyral resin were dispersed together with 50 parts by weight of cyclohexanone using a sand glider. The resulting dispersion was applied onto aluminized mylar having a thickness of 100 μm using a film applicator so that the dry film thickness would be 0.8 g / m ^2, and then dried to form a charge generation layer. 40 parts by weight of the amino compound [50], 20 parts by weight of a polycarbonate resin (m: n = 1: 1) having a molecular weight of 20000 represented by the above chemical formula (II-6), and the above chemical formula (II-6) 50 parts by weight of a polycarbonate resin having a molecular weight of 40,000 (m: n = 1: 1) is dissolved in 500 parts by weight of tetrahydrofuran to give a dry film thickness of 2
It was applied by dip coating so as to have a thickness of 0 μm, and dried to form a charge transport layer, to prepare a laminated photoreceptor having a photosensitive layer composed of two layers. The respect to the electrophotographic photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 1. The results are shown in Table 3.

Examples 22 to 25 The same as Example 1 except that the amino compounds [51], [57], [61] and [63] were used in place of the amino compound [50] used in Example 21. Four types of laminated photoconductors were produced by the method. For each of the photosensitive member in the same manner as in Example 1 were measured _{V 0, E 1/2,} DDR 1, The results are shown in Table 3 and Table 4.

Example 26 On the charge generation layer of Example 1, 30 parts by weight of an amino compound [68] was used as a charge transport material, and a polycarbonate resin (m: n) represented by the general formula (II-1) and having a molecular weight of 40,000 was used. =
4: 1) 50 parts by weight and methyl methacrylate resin (BR
-85; manufactured by Mitsubishi Rayon Co., Ltd.) A solution prepared by dissolving 20 parts by weight in 500 parts by weight of tetrahydrofuran has a dry film thickness of 20.
It was coated so as to have a thickness of μm and dried to form a charge-transporting layer, to prepare a photoreceptor having a photosensitive layer composed of two layers.
For this photoconductor, V ₀ , E
_1/2, to measure the DDR _1, and the results are shown in Table 4.

Example 27 On the charge generation layer of Example 1, 40 parts by weight of an amino compound [10] was used as a charge transport material, and a polycarbonate resin (m: n) having a molecular weight of 40,000 represented by the general formula (II-5) was used. =
1: 1) 60 parts by weight and polyester resin (Byron 2
00; manufactured by Toyobo Co., Ltd.) 10 parts by weight dissolved in 500 parts by weight of tetrahydrofuran is applied to a dry film thickness of 20 μm and dried to form a charge transport layer.
A photoreceptor having a photosensitive layer composed of two layers was produced. _{V 0, E 1/2,} DD in the same manner as in Example 1. The photosensitive member
R ₁ was measured and the results are shown in Table 4.

Example 28 On the charge generation layer of Example 1, as a charge transport material, 50 parts by weight of an amino compound [12] and a polycarbonate resin (m: n) having a molecular weight of 26000 represented by the general formula (II-16) were used.
= 1: 1) A solution prepared by dissolving 70 parts by weight of tetrahydrofuran in 500 parts by weight of tetrahydrofuran is applied to a dry film thickness of 20 μm and dried to form a charge transport layer, which has a photosensitive layer consisting of two layers. A photoconductor was prepared. The respect to the electrophotographic photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 1. The results are shown in Table 4.

Example 29 On the charge generation layer of Example 1, as a charge transport material, 50 parts by weight of an amino compound [16] and a polycarbonate resin (m: n) represented by the general formula (II-12) and having a molecular weight of 36000 were used.
= 1: 1) A solution prepared by dissolving 70 parts by weight of tetrahydrofuran in 500 parts by weight of tetrahydrofuran is applied to a dry film thickness of 20 μm and dried to form a charge transport layer, which has a photosensitive layer consisting of two layers. A photoconductor was prepared. The respect to the electrophotographic photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 1. The results are shown in Table 4.

Example 30 On the charge generation layer of Example 1, as a charge transport material, 20 parts by weight of an amino compound [3], 20 parts by weight of an amino compound [12] and the above general formula (II-4) are shown. Molecular weight 350
A solution prepared by dissolving 70 parts by weight of a polycarbonate resin (m: n = 3: 1) of 00 in 500 parts by weight of tetrahydrofuran is applied to a dry film thickness of 20 μm and dried to form a charge transport layer. A photoreceptor having a photosensitive layer composed of layers was prepared. The respect to the electrophotographic photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 1. The results are shown in Table 4.

Example 31 40 parts by weight of an amino compound [12] was used as a charge transport material on the charge generation layer of Example 1, and a polycarbonate resin (m: n) having a molecular weight of 25,000 represented by the general formula (II-5) was used. =
1: 1) 30 parts by weight and a polycarbonate resin represented by the general formula (II-8) and having a molecular weight of 40,000 (m: n = 4:
1) A solution prepared by dissolving 30 parts by weight of dichloroethane in 500 parts by weight is applied so that the dry film thickness becomes 20 μm, and dried to form a charge transport layer to form a photoreceptor having a photosensitive layer composed of two layers. It was made. About this photoconductor Example 1
Measured _{V 0, E 1/2,} DDR 1 in the same manner as the results are shown in Table 4.

Comparative Examples 1 to 6 Six types of laminated type photoconductors were produced in the same manner as in Example 1 except that the resin shown below was used instead of the resin used in the charge transport layer in Example 1. . In each of the photoreceptor same method as in Example _{1, V 0, E 1/2} , DD
R ₁ was measured and the results are shown in Table 4.

[0099]

[Table 2]

Comparative Examples 7 to 10 Instead of the amino compound [2] used in Example 1, the following amino compounds (2-1), (2-2), (2-3) and (2-
4):

[Chemical 37] Five types of laminated-type photoconductors were produced in the same manner as in Example 1 except that was used. Example 1 for each photoconductor
And measuring the _{V 0, E 1/2,} DDR 1 in the same way, The results are shown in Table 4.

[0101]

[Table 3]

[0102]

[Table 4]

[0103]

[Table 5]

[0104]

EFFECTS OF THE INVENTION By using a specific polycarbonate resin in combination with a specific amino compound, it is possible to obtain a high-sensitivity photoconductor having excellent coating properties, cleaning properties, abrasion resistance and durability, little fatigue deterioration due to repeated use. Could be provided.

Claims (1)

[Claims] 1. A laminate type photoreceptor having a charge generation layer and a charge transport layer provided on a conductive support, wherein the charge transport layer is represented by the following general formula [I]: [In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an alkyl group, an aralkyl group, an aryl group, a biphenyl group or a heterocyclic group which may have a substituent; R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; and X is (Wherein R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group)] and at least one amino compound represented by the following general formula [II]: [Wherein R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom; R ₁₁ and R _12's each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group or an aryl group which may have a substituent;
₁₁ and R ₁₂ and the carbon atom to which they are bonded may together form a ring; m is 0 to 50
0 and n represent a number of 5 to 100; R ₁₇ , R ₁₈ , R ₁₉ , and R
₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently
Which represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom].