JPH05289374A - Lamination type photosensitive body - Google Patents

Abstract

PURPOSE:To improve coating property, cleaning property, wear resistance and durability and to reduce fatigue degradation at the time of repeating use by using a specific polycarbonate resin in the combination of an amino compound. CONSTITUTION:At least one kind of the amino compound expressed by a formula I and at least one kind of the polycarbonate resin expressed by a formula II is contained in a charge transfer layer. In the formula I each of Ar1-Ar4 is an alkyl or aralkyl group, each of R1-R3 is hydrogen atom, an alkyl group, alkoxyl group or the like, X is expressed by a formula III and in the formula III, each of R4-R6 is hydrogen atom, an alkyl group or the like. In the formula II, each of R7-R10 and R13-R16 is hydrogen atom, an alkyl group, an aryl group or the like and when both R11 and R12 are methyl group, all of R7-R10 and R13-R16 are not hydrogen atom. And R11 and R12 are alkyl group, cyclic alkyl group or the like, respectively, (m) is 0-10 molar numbers and (n) is 10-1000 molar numbers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a charge transporting material used for forming a charge transporting layer and a charge transporting material used for forming the charge transporting layer in a laminated type photoreceptor having a charge generating layer and a charge transporting layer provided on a conductive support. The present invention relates to a combination of binder resins.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive member, 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 typified 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 with high sensitivity and repeated stability,
A function-separated photoreceptor having excellent durability has been developed. The function-separated type photoreceptor has a photosensitive layer in which a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are laminated, or a charge generating material and a charge transporting 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 on the photoconductor, poor cleaning of the photoconductor surface, deterioration due to humidity or ozone, and the like cause uneven density on the image. When several hundred 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 repeat stability, such a problem becomes serious, and a photoconductor which can be suitably used also in a laser printer or the like is demanded. Came to be.

The above-mentioned problems are largely due to the coating state of the photosensitive layer, particularly the charge transport layer, for example, coating accuracy and scratches, abrasion and deterioration due to mechanical and physical external force during printing. However, 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.

[0008]

However, in the case of using a charge transport material that does not match well with the binder resin,
The coating liquid of the composition has poor coatability, so-called "repelling" is likely to occur in the photosensitive layer, and white spots are generated in the copied image ("repelling" means a crater-like recessed portion on the coated surface during coating of the photosensitive layer. Means a phenomenon that occurs). 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.

Therefore, an object of the present invention is to solve the above-mentioned problems and to use a charge transport layer in which a specific binder resin and a specific charge transport material are combined, whereby high sensitivity, cleaning property and abrasion resistance are obtained. Another object of the present invention is to provide a photoreceptor having excellent durability, little fatigue against repeated use, and stable electrophotographic characteristics.

[0010]

In a laminated type photoreceptor having a charge generating layer and a charge transporting layer provided on a conductive support, the charge transporting layer is at least one kind represented by the following general formula [I]. An amino compound,

[0011]

[Chemical 4]

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each represent an optionally substituted alkyl group, aralkyl group, aryl group, biphenyl group or heterocyclic group.
R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. X is

[0013]

[Equation 2]

Represents However, R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. ) A multi-layer type photoreceptor containing at least one polycarbonate resin represented by the following general formula [II] or [III] as a binder resin.

[0015]

[Chemical 5]

(Wherein R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R
₁₄ , R ₁₅ and R ₁₆ are a hydrogen atom, an alkyl group, an aryl group,
Represents a halogen atom. However, when R ₁₁ and R ₁₂ are both methyl groups, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ , R ₁₅ , R _15
16 does not take all hydrogen atoms. R ₁₁ and R ₁₂ represent an alkyl group, a cyclic alkyl group or an aryl group which may have a substituent, and R ₁₁ and R ₁₂ may form a cyclic alkyl group which may have a substituent. Also, m is 0 to 100 and n is 10.
Indicates a number of moles of ~ 1000. )

[0017]

[Chemical 6]

(Wherein R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ ,
R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ represent a hydrogen atom, an alkyl group, a halogen atom or an aryl group which may have a substituent. p is 0 to 100 and q is 10 to 1000. ) The charge transport material used in the charge transport layer of the photoreceptor of the present invention contains at least one amino compound represented by the general formula [I].

All the amino compounds represented by the above formula [I] are asymmetric with respect to X and have poor crystallinity.
Shows good compatibility with binder resins. From the viewpoint of sensitivity, it is desirable that at least one of Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ can have 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 [IV]:

[0022]

[Chemical 7]

[Wherein R ₁ , R ₂ , R ₃ and X are represented by the general formula
Same meaning as that of [I]. ] An iodine compound represented by
The following general formulas [V] and [VI]:

[0024]

[Chemical 8]

[In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ have the same meanings as those in formula [I]. ] The amino compound represented by the above can be synthesized by the Ullmann reaction in the presence of a basic compound or a transition metal compound catalyst and a solvent.

The reaction is generally 100 to 25 under normal pressure.
It is carried out at a temperature of 0 ° C., but it may be carried out under pressure. After the completion of the reaction, the solid matter that has broken out into the reaction solution can be removed, and then the solvent can be 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 preferably used. Furthermore, from the viewpoint of reaction rate and thermal stability, carbonates and hydrogen carbonates of alkali metals 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 and F.
Metals such as e, 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,
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, nitric acid Cupric, copper carbonate, cuprous acetate,
Cupric acetate and the like are preferred. Among them, especially CuCl, C
uCl ₂ , CuBr, CuBr ₂ , CuI, CuO, Cu ₂ O, Cu
SO 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.

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

[0049]

[Chemical 27]

[0050]

[Chemical 28]

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 is a diol compound represented by the following general formulas [VII] and [VIII]. Can be used for copolymerization by using a general polycarbonate synthesis method such as the phosgene method.

[0052]

[Chemical 29]

(In the formula, R _{7 to} R ₁₆ have the same meaning as [II].) Further, the polycarbonate resin represented by the general formula [III] is
It can be synthesized by copolymerizing a diol compound represented by the following general formulas [X] and [XI] by a general polycarbonate synthesis method such as a phosgene method.

Examples of the polycarbonate resin represented by the general formula [II] or [III] used in the photoreceptor of the present invention include those shown below.

[0055]

[Chemical 30]

[0056]

[Chemical 31]

[0057]

[Chemical 32]

[0058]

[Chemical 33]

[0059]

[Chemical 34]

[0060]

[Chemical 35]

[0061]

[Chemical 36]

In the present invention, from the viewpoint of durability and coatability, 1 × 10 ⁴ to 1 × 10 ⁵ , preferably 2 × 10 ⁴ to 8 composed of various repeating units as described above are used.
× Using the polycarbonate resin having a number average molecular weight of 10 ^4, more preferably 2 to 4 × 10 ⁴ and 4-6.
A polycarbonate resin having a number average molecular weight of 5 × 10 ⁴ is mixed and used. When the number average molecular weight is less than 1 × 10 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 may be used in combination with other resins. When the content of the polycarbonate resin is less than 50% by weight based on the total weight of the resin in the charge generation layer, the hardness of the film itself is lowered, the durability is deteriorated, and the sensitivity is lowered. To use. Examples of the resin that can be used in combination with the polycarbonate resin include polystyrene resin, polymethylmethacrylate resin, polyester resin, polyarylate resin, and phenoxy resin.

The case of forming the multi-layer photosensitive member according to the present invention in which the charge generating layer and the charge transport layer are laminated on the conductive support will be specifically described below.

The laminated type photoreceptor of the present invention comprises a charge transport layer formed by combining the amino compound and a polycarbonate resin.

The laminated type 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 film 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.

On the charge generation layer thus formed, an amino compound represented by the general formula [I] as a charge transport material and a general formula [II] or [III] as a binder resin.
A solution in which a polycarbonate resin represented by the above is dissolved in an appropriate solvent is applied and dried to form a charge transport layer, and the laminated type photoreceptor of the present invention is produced. At this time, the thickness of the charge transport layer is 3
It is desirable that the thickness is -40 μm, preferably 5-30 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. Further, an antioxidant, a sensitizer, a thickener, a surfactant, an anti-curl agent, an ultraviolet absorber, a plasticizer, a leveling agent and the like which are known per se may be added to the charge transport layer.

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 is provided. It is possible to improve the property of injecting charge from the photosensitive layer to the photosensitive layer.

Polyimide, polyamide, nitrocellulose polyvinyl butyral, polyvinyl alcohol, aluminum oxide and the like are suitable as the material used for the intermediate layer, 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, and Group III and Group V atoms 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, the charge transport layer and the charge generation layer on the 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 copper, aluminum, iron, nickel or the like is used. In addition, these metals are attached to a plastic film by vacuum deposition, electroless plating, etc.,
Alternatively, a layer of a conductive compound such as a conductive polymer, indium oxide, tin oxide or the like, which is similarly provided by coating or vapor deposition on a support such as paper or a plastic film, can be used.

Examples of the charge generating material used in the photoreceptor of the present invention include bisazo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes. Organic substances such as dyes, azo dyes, quiadrin dyes, indigo dyes, perylene dyes, polycyclic quinone pigments, bisbenzimidazole pigments, indathlon pigments, squarylium pigments, phthalocyanine pigments, and pyrrolopyrrole pigments Inorganic substances such as selenium, selenium / tellurium, selenium / arsenic, cadmium sulfide, 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.

The binder resin used in the present invention is preferably electrically insulating and has a volume resistance of 1 × 10 ¹² Ω · cm or more when measured alone. For example, known thermoplastic resins, thermosetting resins, photocurable resins,
A binder such as a photoconductive resin 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-
Thermoplastic resins such as vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin,
Thermosetting resin such as urethane resin, silicone resin, phenol resin, melamine resin, xylene resin, alkyd resin, and thermosetting acrylic resin; photocurable resin; photoconductivity such as polyvinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylpyrrole Resins and the like can be used, and these binder resins can be used alone or in combination of two or more kinds.

The photoreceptor of the present invention comprises a binder resin and a plasticizer such as halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutyl phthalate, O-terphenyl, chloranil, tetracyanoethylene, 2,4,7-.
Electron withdrawing sensitizers such as trinitrofluorenone, 5,6-dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride, 3,5-dinitrobenzoic acid, methyl violet, rhodamine B, cyanine dye, pyrylium salt, A sensitizer such as thiapyrylium salt may be used.

The solvent for dissolving these resins varies depending on the kind of the resin, but for example, alcohols such as methanol, ethanol and iso-propyl alcohol,
Ketones such as acetone, methyl ethyl ketone and cyclohexane, amides such as N, N-dimethylformamide and 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.

[0078]

[Synthesis Example] The synthesis method of the amino compound represented by the above-mentioned amino compound example [4] is shown below. 4-iododiphenyl-
50 g (0.10 mol) of 4'-p-iodobenzyl, 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.
The filtrate was separated by silica gel column chromatography, and 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.

[0080]

[Table 1]

[0081]

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

[0083]

[Chemical 37]

0.45 parts by weight of the bisazo compound represented by the general formula (V), polyester resin (Vylon 200,
0.45 parts by weight of Toyo Boseki Co., Ltd. and 50 parts by weight of cyclohexanone were dispersed using a sand mill. The resulting dispersion of the bisazo compound was applied onto a 100 μm thick aluminized mylar using a film applicator so that the dry film thickness was 0.3 g / m ^2, and then dried to form a charge generation layer. On this, 50 parts by weight of the amino compound [3] and 70 parts by weight of the polycarbonate resin represented by the chemical formula (1-1) (m and n are about 40), 400 parts by weight of 1,4-dioxane and 100 parts by weight of cyclohexanone are added. The solution dissolved in each part was applied so as to have a dry film thickness of 20 μm, and dried to form a charge transport layer, thereby manufacturing a laminated type photoreceptor having a photosensitive layer composed of two layers.

The thus prepared photoconductor is a commercially available electrophotographic copying machine (EP-470Z manufactured by Minolta Camera Co., Ltd.).
Built-in -6 Kv and charged by corona discharge to obtain an initial surface potential V ₀ (v) and an exposure amount necessary for the surface potential to be attenuated to half of the initial surface potential (hereinafter, half-exposure amount) E
The decay rate DDR ₁ (%) of the initial potential when left in the dark for _1/2 (Lux · sec) for 1 second was measured. The results are shown in Table 3.

Further, the photoconductor of Example 1 and the photoconductors of Examples 2 and 28 and Comparative Examples 1, 2, 5 and 6 described later are commercially available electrophotographic copying machines (E manufactured by Minolta Camera Co., Ltd.).
P-5400) was repeatedly photographed during negative charging. V _0, E _1/2 in 10,000 sheets Stock back and forth with each photoreceptor, and measuring the residual potential V _R (v) and the film thickness,
The results are shown in Table 6. In addition, the image characteristics after the actual copying of 10,000 sheets were evaluated.

In the photoconductors of Examples 1, 2, and 11,
It was confirmed that the final image was excellent in gradation as well as the initial image, a clear image was obtained without sensitivity change, 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 photoreceptors were produced by the method. For each of the photoconductors, V ₀ , E _1/2 ,
DDR ₁ was measured and the results are shown in Table 3.

Example 6

[0090]

[Chemical 38]

0.45 part by weight of the bisazo compound represented by the general formula (VI) and 0.45 part by weight of polyvinyl butyral were dispersed in a sand mill together with 50 parts by weight of cyclohexanone. Thickness of the obtained dispersion of bisazo compound is 1
A charge applicator layer was formed by applying a dry film thickness of 0.3 g / m ² onto a 00 μm aluminized mylar using a film applicator and then drying. On top of this, 40 parts by weight of the amino compound [12] and the polycarbonate resin (m≈50, n≈100) 60 represented by the above chemical formula (1-4).
And 500 parts by weight of 1,4-dioxane are applied by dip coating to a dry film thickness of 20 μm.
A charge transport layer was formed by drying to prepare a photoreceptor having a photosensitive layer composed of two layers. V ₀ , E _1/2 and DDR ₁ of this photoreceptor were measured in the same manner as in Example 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 instead of the diamino compound [12] used in Example 6. Four types of laminated photoreceptors were produced by the method. For each of the photoconductors, V in the same manner as in Example 1
₀ , E _1/2 and DDR ₁ were measured and 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 onto a 100 μm thick aluminized mylar using a film applicator so that the dry film thickness would be 0.2 g / m ^2, and then dried to form a charge generation layer. A solution prepared by dissolving 40 parts by weight of the amino compound [25] and 60 parts by weight of the polycarbonate resin (m = 0, n≈100) represented by the chemical formula (1-10) in 500 parts by weight of dichloroethane was dried on Is 25 μm
Was applied and dried to form a charge transporting layer, to prepare a laminated type photoreceptor having a photosensitive layer composed of two layers. For this photosensitive member, V ₀ ,
E _1/2 and DDR ₁ were measured, 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 instead of the distyryl compound [25] used in Example 11. Four types of laminated photoreceptors 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 Titanyl phthalocyanine pigment 0.5 part by weight, phenoxy resin 0.2 part by weight and polyvinyl butyral resin 0.3.
Parts by weight were 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 0.25.
The charge generation layer was formed by applying the coating solution so that the coating amount was g / m ² and then drying. 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 above chemical formula (1-13) and the above chemical formula (1-13) A solution of 45 parts by weight of a polycarbonate resin having a molecular weight of 45,000 (m = 0) in 400 parts by weight of 1,4-dioxane and 100 parts by weight of cyclohexanone was applied to a dry film thickness of 20 μm and dried. A charge transport layer was formed to prepare a laminated type photoreceptor having a photosensitive layer composed of two layers. V ₀ , E _1/2 and DDR ₁ of this photoreceptor were measured in the same manner as in Example 1, and the results are shown in Table 3.

Examples 17 to 20 The same as Example 16 except that the amino compounds [39], [45], [48] and [49] were used in place of the amino compound [38] used in Example 16. Four types of laminated photoreceptors were produced by the method. For each of the photoconductors, V in the same manner as in Example 1
₀ , E _1/2 and DDR ₁ were measured and the results are shown in Table 4.

Example 21 0.5 parts by weight of dibromoanthanthrone and 0.5 parts by weight of polyvinyl butyral resin were dispersed together with 50 parts by weight of cyclohexanone using a sand grinder. The obtained dispersion was dried on a 100 μm thick aluminized mylar using a film applicator to give a dry film thickness of 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 chemical formula (1-8), and the chemical formula (1-1) 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. V ₀ , E _1/2 and DDR ₁ of this photoreceptor were measured in the same manner as in Example 1, and the results are shown in Table 4.

Examples 22 to 25 The same procedure as in Example 1 except that the amino compounds [51], [57], [61] and [63] were used in place of the amino compound [50] used in Examples 21. Then, four kinds of laminated photoconductors were produced. V ₀ , E _1/2 and DDR ₁ of each photoconductor were measured by the same method as in Example 1 and the results are shown in 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 = 40) having a molecular weight of 40,000 represented by the general formula (1-13).
0) 50 parts by weight and methyl methacrylate resin (BR-
85, made by Mitsubishi Rayon) 20 parts by weight dissolved in 500 parts by weight of tetrahydrofuran to give a dry film thickness of 20 μm
Was applied and dried to form a charge transport layer, to prepare a photoreceptor having a photosensitive layer composed of two layers. For this photoconductor, V ₀ , E _1/2 ,
DDR ₁ was measured 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) represented by the general formula (1-1) and having a molecular weight of 40,000 was used.
= 1: 1) 60 parts by weight and a polyester resin (Vylon 200, manufactured by Toyobo) 10 parts by weight dissolved in 500 parts by weight of tetrahydrofuran are applied so as to have a dry film thickness of 20 μm, and dried to form a charge transport layer. To form
A photoreceptor having a photosensitive layer composed of two layers was produced. With respect to this photosensitive member, V ₀ , E _1/2 and DD were applied in the same manner as in Example 1.
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) represented by the general formula (2-1) and having a molecular weight of 26000 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. V ₀ , E _1/2 and DDR ₁ of this photoreceptor were measured in the same manner as in Example 1, and 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) having a molecular weight of 36000 represented by the above general formula (2-3) 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. V ₀ , E _1/2 and DDR ₁ of this photoreceptor were measured in the same manner as in Example 1, and 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 (2-4) are shown. Molecular weight 3500
A solution prepared by dissolving 70 parts by weight of a polycarbonate resin of 0 (m: n = 2: 3) in 500 parts by weight of tetrahydrofuran,
It was applied so that the dry film thickness would be 20 μm, and dried to form a charge transport layer, to prepare a photoreceptor having a photosensitive layer composed of two layers. V ₀ , E _1/2 and DDR ₁ of this photoreceptor were measured in the same manner as in Example 1, and 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 = 0) having a molecular weight of 25,000 represented by the general formula (1-2) was used. )
A solution prepared by dissolving 30 parts by weight and 30 parts by weight of a polycarbonate resin represented by the general formula (2-8) and having a molecular weight of 40,000 in 500 parts by weight of dichloroethane had a dry film thickness of 2
It was applied so as to have a thickness of 0 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 and DDR ₁ were measured, and the results were obtained as in Example 1 except that the resin shown below was used instead of the resin used in the charge transport layer in Comparative Examples 1 to 6 Example 1 shown in Table 4. Six types of laminated photoreceptors were manufactured by the same method. For each of the photoconductors, V ₀ , E _1/2 , DD was applied in the same manner as in Example 1.
R ₁ was measured and the results are shown in Table 5.

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[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-
Five types of laminated type photoreceptors were produced in the same manner as in Example 1 except that 4) was used. Further, V ₀ , E _1/2 and DDR ₁ were measured for each photoreceptor in the same manner as in Example 1 and the results are shown in Table 5.

[0107]

[Chemical Formula 39]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

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

[0113]

Front page continuation (72) Inventor Yuki Shimada 2-3-13 Azuchi-cho, Chuo-ku, Osaka Osaka International Building Minolta Camera Co., Ltd.

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 comprises at least one amino compound represented by the following general formula [I]: Chemical 1] (In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each 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 , R ₃ is a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and X is Represents. However, R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. ) A multi-layer type photoreceptor containing at least one polycarbonate resin represented by the following general formula [II] or [III] as a binder resin. [Chemical 2] (In the formula, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ , R ₁₅ , R _15
16 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, when both R ₁₁ and R ₁₂ are methyl groups,
_{R 7, R 8, R 9} , R 10, R 13, R 14, R 15, R 16 do not take all hydrogen atoms. R ₁₁ and R ₁₂ represent an alkyl group, a cyclic alkyl group or an aryl group which may have a substituent,
₁₁ and R ₁₂ may form a cyclic alkyl group which may have a substituent. Also, m is 0 to 100 and n is 10 to 1000.
The number of moles of ) [Chemical 3] (In the formula, R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ ,
R ₂₄ and R ₂₅ represent a hydrogen atom, an alkyl group, a halogen atom or an aryl group which may have a substituent. p is 0 to 1
00 and q show the number of moles of 10 to 1000. )