JP4141489B2 - Electrophotographic photoreceptor - Google Patents

Description

  The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor excellent in photosensitivity, printing characteristics, and repeated use characteristics using a specific charge transport material in combination.

  In an organic electrophotographic photosensitive member, a function-separated type photosensitive member in which a charge generation layer and a charge transport layer are laminated has been noticed and put into practical use in order to increase the sensitivity. The mechanism of electrostatic latent image formation in this function-separated type photoreceptor is that when the photoreceptor is charged and then irradiated with light, the light is absorbed by the charge generation layer, and the charge generation layer that has absorbed the light generates charge carriers. This charge carrier is injected into the charge transport layer, moves in the charge transport layer (or photosensitive layer) according to the electric field generated by charging, and forms an electrostatic latent image by neutralizing the charge on the surface of the photoreceptor. To do.

  Various photoconductor materials have been developed so far, but in order to make them excellent electrophotographic photoconductors that can be put into practical use, sensitivity, receptive potential, potential holding property, potential stability, residual potential, and spectral characteristics are required. Various characteristics such as representative electrophotographic characteristics, mechanical durability such as abrasion resistance, chemical stability against heat, light, discharge products, and the like are required. In particular, it is important to have high sensitivity and excellent repeated stability. However, as described above, a certain degree of high sensitivity characteristics can be achieved by a combination of an appropriate charge generation material and charge transport material. is there.

  On the other hand, in addition to this, studies have been made on the combination of mechanical durability, but depending on the combination of conventionally proposed charge generation materials and charge transport materials, a material that satisfies all of the above conditions can be obtained. It was not done. Therefore, there has been a strong demand for the completion of an electrophotographic photosensitive member that maintains high sensitivity and is excellent in stability by repeated use by using conventionally proposed charge generation materials and charge transport materials.

  The object of the present invention is to improve the film quality of the photoreceptor and prevent the occurrence of abnormal images due to deterioration of the photosensitive layer film, thereby exhibiting excellent stability even after repeated use and maintaining high sensitivity. It is to provide an electrophotographic photosensitive member that can be used.

  According to the present invention, first, a charge generation layer containing a charge generation material as a main component on a conductive support, a compound represented by the following general formula (1), and a compound represented by the following general formula (4): There is provided an electrophotographic photosensitive member characterized in that a charge transport layer is contained.

式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は、水素原子、置換もしくは無置換の低級アルキル基または置換もしくは無置換のアリール基を、Ａｒ_１は置換もしくは無置換のアリール基を、Ａｒ_２は置換もしくは無置換のアリーレン基を表す。また、Ａｒ_１とＲ_１は共同で環を形成してもよく、ｎは０または１の整数である。

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group, Ar ₁ is a substituted or unsubstituted aryl group, Ar ₂ represents a substituted or unsubstituted arylene group. Ar ₁ and R ₁ may form a ring together, and n is an integer of 0 or 1.

式中、Ｒ_１、Ｒ_２は、水素原子、ハロゲン原子、ニトロ基、シアノ基または置換もしくは無置換のアルキル基、Ｒ_３、Ｒ_４は、水素原子、シアノ基、アルコキシカルボニル基または置換もしくは無置換のアルキル基、Ｒ_５は、水素原子、低級アルキル基またはアルコキシ基を表す。ｊは１〜５、ｋは１〜４、ｌは０〜２、ｍは１または２、ｎは１〜３の整数を表す。Ｗは、ｍが１である場合、水素原子または構造式

で示される官能基であり、ｍが２である場合、構造式

で示される官能基である。
第二に、導電性支持体上に、下引き層、上記電荷発生層、上記電荷輸送層が積層されていることを特徴とする電子写真感光体が提供される。
第三に、導電性支持体がアルミニウム製支持体であることを特徴とする電子写真感光体が提供される。
第四に、導電性支持体上に少なくとも電荷発生材料と下記一般式（１）で示される化合物と下記一般式（４）で示される化合物を含有する単層感光層が設けられていることを特徴とする電子写真感光体が提供される。

In the formula, R ₁ and R ₂ are a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a substituted or unsubstituted alkyl group, and R ₃ and R ₄ are a hydrogen atom, a cyano group, an alkoxycarbonyl group, or a substituted or unsubstituted group. A substituted alkyl group, R ₅ represents a hydrogen atom, a lower alkyl group or an alkoxy group . j represents 1 to 5, k represents 1 to 4, l represents 0 to 2, m represents 1 or 2, and n represents an integer of 1 to 3. W is a hydrogen atom or a structural formula when m is 1

And when m is 2, the structural formula

It is a functional group shown by.
Second, an electrophotographic photosensitive member is provided in which an undercoat layer, the charge generation layer, and the charge transport layer are laminated on a conductive support.
Third, an electrophotographic photosensitive member is provided in which the conductive support is an aluminum support.
Fourth, a single-layer photosensitive layer containing at least a charge generating material, a compound represented by the following general formula (1) and a compound represented by the following general formula (4) is provided on the conductive support. A featured electrophotographic photoreceptor is provided.

式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は、水素原子、置換もしくは無置換の低級アルキル基または置換もしくは無置換のアリール基を、Ａｒ_１は置換もしくは無置換のアリール基を、Ａｒ_２は置換もしくは無置換のアリーレン基を表す。また、Ａｒ_１とＲ_１は共同で環を形成してもよく、ｎは０または１の整数である。

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group, Ar ₁ is a substituted or unsubstituted aryl group, Ar ₂ represents a substituted or unsubstituted arylene group. Ar ₁ and R ₁ may form a ring together, and n is an integer of 0 or 1.

式中、Ｒ_１、Ｒ_２は、水素原子、ハロゲン原子、ニトロ基、シアノ基または置換もしくは無置換のアルキル基、Ｒ_３、Ｒ_４は、水素原子、シアノ基、アルコキシカルボニル基または置換もしくは無置換のアルキル基、Ｒ_５は、水素原子、低級アルキル基またはアルコキシ基を表す。ｊは１〜５、ｋは１〜４、ｌは０〜２、ｍは１または２、ｎは１〜３の整数を表す。Ｗは、ｍが１である場合、水素原子または構造式

で示される官能基であり、ｍが２である場合、構造式

で示される官能基である。
第五に、導電性支持体上に、下引き層、上記単層感光層が積層されている電子写真感光体が提供される。
第六に、導電性支持体がアルミニウム製支持体であることを特徴とする電子写真感光体が提供される。

In the formula, R ₁ and R ₂ are a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a substituted or unsubstituted alkyl group, and R ₃ and R ₄ are a hydrogen atom, a cyano group, an alkoxycarbonyl group, or a substituted or unsubstituted group. A substituted alkyl group, R ₅ represents a hydrogen atom, a lower alkyl group or an alkoxy group . j represents 1 to 5, k represents 1 to 4, l represents 0 to 2, m represents 1 or 2, and n represents an integer of 1 to 3. W is a hydrogen atom or a structural formula when m is 1

And when m is 2, the structural formula

It is a functional group shown by.
Fifth, on an electroconductive support, an undercoat layer, an electrophotographic photoreceptor upper Kitanso photosensitive layer is laminated is provided.
Sixth, an electrophotographic photosensitive member is provided in which the conductive support is an aluminum support.

  As described above, by combining the specific charge transporting material as described above, high stability can be obtained without losing high sensitivity, and abnormal images based on deterioration of the photosensitive layer such as cracks can be generated even by repeated use. The electrophotographic photoreceptor shown is obtained.

  The present invention is described in detail below. As a result of repeated studies on the above problems, the present inventors have used the above-mentioned specific combination of charge transport materials for the photosensitive layer, so that the occurrence of image quality defects can be suppressed even after repeated use, and excellent electrophotographic characteristics can be achieved. The present inventors have found that an electrophotographic photosensitive member can be obtained, and have reached the present invention.

  The electrophotographic photosensitive member of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view showing a single-layer photosensitive member in the present invention, and a photosensitive layer 15 is provided on a conductive support 11. . 2 and 3 are cross-sectional views showing examples of the structure of the laminated photoconductor according to the present invention, a charge generation layer 17 mainly composed of a charge generation material, and a charge transport layer 19 mainly composed of a charge transport material. However, it has a laminated structure. In such a single layer or multilayer photoreceptor, a charge transport material comprising the compound represented by the general formula (1) and at least one selected from the compounds represented by the general formulas (2) to (4) is provided. Used in combination.

Embodiments of the invention will be described below. The conductive support 11 has a volume resistance of 10 ¹⁰ Ωcm or less, for example, a metal such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum, or a metal such as tin oxide or indium oxide. Oxide coated by film or cylindrical plastic or paper by vapor deposition or sputtering, or aluminum, aluminum alloy, nickel, stainless steel, etc. and their raw material, then cut, superfinished, polished It is possible to use a tube that has been surface-treated.

  Next, the photosensitive layer 15 will be described. For convenience of explanation, the case where the charge generation layer 17 and the charge transport layer 19 are laminated will be described first. The charge generation layer 17 is a layer mainly composed of a charge generation material. Inorganic and organic materials are used as charge generation materials, and representative examples thereof include monoazo pigments, disazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments, quinone condensed polycyclic compounds, squaric acid dyes. Phthalocyanine pigments, naphthalocyanine pigments, azulenium salt dyes, selenium, selenium-tellurium, selenium-arsenic alloys, amorphous silicon, and the like.

  The charge generation material may be used alone or in combination of two or more. The charge generation layer 17 is dispersed by a ball mill, an attritor, a sand mill, or the like using a suitable solvent such as tetrahydrofuran, cyclohexanone, dioxane, 2-butanone, dichloroethane, or the like, together with a binder resin in which a charge generation material is used as appropriate. It can be formed by coating. The coating can be performed using a dip coating method, a spray coating method, a bead coating method, or the like.

  Suitable binder resins include polyamide, polyurethane, polyester, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, and polyacrylamide. The amount of the binder resin used appropriately is suitably 0 to 2 parts by weight with respect to 1 part by weight of the charge generating material.

  The charge generation layer 17 can also be provided by a known vacuum thin film manufacturing method. The film thickness of the charge generation layer 17 is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.

  The charge transport layer 19 can be formed by dissolving or dispersing a charge transport material and a binder resin in an appropriate solvent, and applying and drying the solution. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed.

  As the charge transport material, a compound represented by the above general formula (1) and at least one selected from compounds represented by the general formulas (2) to (4) are mixed and used. Specific examples of these compounds are listed in Tables 1 to 39 below.

これら化合物の混合比は、一般式（１）で示される化合物と一般式（２）〜（４）でそれぞれ示される化合物から選択された少なくとも１種とが、５：９５〜９５：５の範囲にあると良好な結果が得られる。また、これら電荷輸送材料の使用量は、積層感光体では電荷輸送層の全構成材料に対して１５〜７５重量％、好ましくは２５〜６５重量％である。

The mixing ratio of these compounds is such that the compound represented by the general formula (1) and at least one selected from the compounds represented by the general formulas (2) to (4) are in the range of 5:95 to 95: 5. If it is, good results can be obtained. The amount of the charge transport material used is 15 to 75% by weight, preferably 25 to 65% by weight, based on the total constituent materials of the charge transport layer in the laminated photoconductor.

  In addition to a charge transport material composed of a compound represented by the general formula (1) and at least one selected from the compounds represented by the general formulas (2) to (4), a known electron transport charge A transport material and / or a hole transport charge transport material may be used in combination.

  Examples of the binder resin used for the charge transport layer 19 together with the charge transport material include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, and vinyl chloride. -Vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, acrylic resin, silicone resin, epoxy resin, melamine resin And thermoplastic or thermosetting resins such as urethane resin, phenol resin, and alkyd resin.

  As the solvent, tetrahydrofuran, dioxane, toluene, 2-butanone, monochlorobenzene, dichloroethane, methylene chloride and the like are used.

  The thickness of the charge transport layer 19 is suitably 5 to 100 μm.

  In the present invention, a plasticizer or a leveling agent may be added to the charge transport layer 19. As the plasticizer, those used as a plasticizer for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is suitably about 0 to 30% by weight based on the binder resin. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain are used, and the amount used is 0 to 1 weight relative to the binder resin. % Is appropriate.

  Next, the case where the photosensitive layer has a single layer structure (FIG. 1) will be described. Many of the materials used in this case are the same as those used in the functional separation type composed of the charge generation material and the charge transport material.

  That is, a charge transport material comprising at least a charge generating material and at least one compound selected from the compounds represented by the general formulas (2) to (4) and the compound represented by the general formula (1) together with the binder resin is suitable. It can be formed by dissolving or dispersing in an appropriate solvent, coating and drying. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. As the binder resin, the binder resin previously mentioned in the charge transport layer 19 can be used as it is, and the binder resin mentioned in the charge generation layer 17 may be mixed.

  A eutectic complex formed from a pyrylium dye and a bisphenol A polycarbonate comprises a compound represented by the general formula (1) and at least one selected from compounds represented by the general formulas (2) to (4). A photosensitive layer to which a charge transport material is added can also be used as a single-layer photosensitive layer.

  Further, charge generation is performed mainly with a charge transport material and a binder resin composed of a compound represented by the general formula (1) and at least one selected from the compounds represented by the general formulas (2) to (4). A monolayer sensitive layer containing no material as an active ingredient is also useful as a photoreceptor having sensitivity to blue light to ultraviolet light.

  The mixing ratio of the two specific types of charge transport materials in the single-layer photosensitive layer is preferably in the range of 5:95 to 95: 5, as in the case of the laminated photosensitive layer, and the amount used is the total constitution of the single-layer photosensitive layer. It is 5 to 75% by weight, preferably 10 to 65% by weight, based on the material. The film thickness of the single-layer photosensitive layer is suitably 5 to 100 μm.

  In the electrophotographic photoreceptor of the present invention, an undercoat layer can be provided between the conductive support 11 and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is applied with a solvent on these resins, the resin may be a resin having a high resistance to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resins, alkyd-melamine resins, and epoxy resins. Examples thereof include curable resins that form a three-dimensional network structure.

  In addition, metal oxide fine powders exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential. These undercoat layers can be formed using an appropriate solvent and coating method as in the photosensitive layer described above.

  Furthermore, a metal oxide layer formed by, for example, a sol-gel method using a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like is also useful as the undercoat layer of the present invention.

In addition, the undercoat layer of the present invention is provided with Al ₂ O ₃ by anodic oxidation, organic substances such as polyparaxylylene (parylene), SiO, SnO ₂ , TiO ₂ , ITO, CeO _2. A material provided with an inorganic material such as a vacuum thin film can also be used favorably. The thickness of the undercoat layer is suitably from 0 to 5 μm.

  In the electrophotographic photoreceptor of the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. Materials used for this include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, Polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, AS resin, AB resin, BS resin, polyurethane, polyvinyl chloride, polyvinylidene chloride, Resins such as epoxy resins can be used.

  In addition to the protective layer, for the purpose of improving wear resistance, fluorine resin such as polytetrafluoroethylene, silicone resin, and those in which inorganic materials such as titanium oxide, tin oxide and potassium titanate are dispersed in these resins, etc. Can be added. As a method for forming the protective layer, a normal coating method is employed. In addition, about 0.5-10 micrometers is suitable for the thickness of a protective layer. In addition to the above, known materials such as i-C and a-SiC formed by a vacuum thin film manufacturing method can also be used as the protective layer.

  In the present invention, another intermediate layer can be provided between the photosensitive layer and the protective layer. In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a normal coating method is employed as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

  The following examples illustrate the present invention in detail, and the present invention is not limited by the examples. In addition, all the parts in an Example are a weight part. First, the case where the compounds represented by the general formula (1) and the general formula (2) are used in combination as the charge transport material will be described with reference to Examples 1 to 4 and Comparative Examples 1 to 4.

Example 1
On an aluminum cylinder with an outer diameter of 70 mm, an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied and dried to form an undercoat layer of 3 μm and 0.2 μm, respectively. The electrophotographic photosensitive member of the present invention was prepared by forming a charge generation layer of 22 μm and a charge transport layer of 22 μm.
[Undercoat layer coating solution]
Oil-free alkyd resin
(Dainippon Ink Chemical Co., Ltd .: Beckolite M6401) 15 parts
Melamine resin
(Dainippon Ink Chemical Co., Ltd .: Super Becamine G-821) 10 parts
Titanium dioxide (Ishihara Sangyo Co., Ltd .: Taipei R-670) 50 parts
2-butanone 40 parts
[Charge generation layer coating solution]
5 parts of charge generation material of the following structural formula

ポリビニルブチラール樹脂
（電気化学工業社製：デンカブチラール ＃５０００−Ａ） ２部
シクロヘキサノン ２００部
４−メチル−２−ペンタノン １５０部
〔電荷輸送層塗工液〕
化合物ＮＯ．２−２１の化合物 ３部
化合物ＮＯ．１−３の化合物 ６部
ポリカーボネート（帝人化成社製：パンライトＫ−１３００） １０部
テトラヒドロフラン ７５部
比較例１
実施例１の電荷輸送層塗工液を下記組成のものに変えた以外は実施例１と同様にして比較例の電子写真感光体を作製した。
〔電荷輸送層塗工液〕
化合物ＮＯ．２−２１の化合物 ９部
ポリカーボネート
（帝人化成社製：パンライトＫ−１３００） １０部
テトラヒドロフラン ７５部
実施例２
アルミニウムシリンダー表面を陽極酸化処理した後、封孔処理を行った。この上に、下記電荷発生層塗工液、電荷輸送層塗工液を順次塗布・乾燥して各々０．２μｍの電荷発生層、２０μｍの電荷輸送層を形成し本発明の電子写真感光体を作製した。
〔電荷発生層塗工液〕
Ｘ型無金属フタロシアニン
（大日本インキ化学社製：ファストゲンブルー８１２０Ｂ） ３部
ポリビニルブチラール樹脂
（積水化学工業社製：エスレック ＢＬ−Ｓ ） １部
シクロヘキサノン ２５０部
テトラヒドロフラン ５０部
〔電荷輸送層塗工液〕
化合物ＮＯ．２−４７の化合物 ２部
化合物ＮＯ．１−４８の化合物 ８部
ポリカーボネート
（帝人化成社製：パンライトＬ−１２５０） １０部
塩化メチレン ８０部
比較例２
実施例２の電荷輸送層塗工液において、化合物ＮＯ．２−４７の化合物を添加しないこと以外は実施例２と同様にして比較例の電子写真感光体を作製した。

Polyvinyl butyral resin
(Manufactured by Denki Kagaku Kogyo Co., Ltd .: Denka Butyral # 5000-A) 2 parts
200 parts of cyclohexanone
150 parts of 4-methyl-2-pentanone
[Charge transport layer coating solution]
Compound NO. 3-21 compounds 3 parts
Compound NO. 1-3 parts of compound 6 parts
10 parts of polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite K-1300)
Tetrahydrofuran 75 parts Comparative Example 1
A comparative electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transport layer coating solution of Example 1 was changed to one having the following composition.
[Charge transport layer coating solution]
Compound NO. 9-21 compounds of 2-21
Polycarbonate
(Teijin Chemicals: Panlite K-1300) 10 parts
Tetrahydrofuran 75 parts Example 2
After anodizing the surface of the aluminum cylinder, sealing treatment was performed. On top of this, the following charge generation layer coating solution and charge transport layer coating solution are sequentially applied and dried to form a 0.2 μm charge generation layer and a 20 μm charge transport layer, respectively. Produced.
[Charge generation layer coating solution]
X-type metal-free phthalocyanine
(Dainippon Ink Chemical Co., Ltd .: Fastgen Blue 8120B) 3 parts
Polyvinyl butyral resin
(Sekisui Chemical Co., Ltd .: ESREC BL-S) 1 part
250 parts of cyclohexanone
50 parts of tetrahydrofuran
[Charge transport layer coating solution]
Compound NO. 2-47 compounds 2 parts
Compound NO. 1-48 compound 8 parts
Polycarbonate
(Teijin Chemicals: Panlite L-1250) 10 parts
80 parts of methylene chloride Comparative Example 2
In the charge transport layer coating solution of Example 2, compound NO. A comparative electrophotographic photosensitive member was produced in the same manner as in Example 2 except that the compound 2-47 was not added.

Example 3
On the aluminum cylinder, undercoat layer coating solution, charge generation layer coating solution, and charge transport layer coating solution having the following composition are sequentially applied and dried to form a 2 μm undercoat layer and a 0.2 μm charge generation layer, respectively. A 20 μm charge transport layer was formed to produce an electrophotographic photoreceptor of the present invention.
[Undercoat layer coating solution]
Alcohol soluble nylon
(Toray Industries, Inc .: Amilan CM-8000) 10 parts
Titanium dioxide (Ishihara Sangyo Co., Ltd .: Taipei CR-EL) 40 parts
120 parts of methanol
60 parts of n-butanol
[Charge generation layer coating solution]
3 parts of charge generation material of the following structural formula

ポリエステル（東洋紡社製：バイロン ２００） １部
シクロヘキサノン １５０部
シクロヘキサン １００部
〔電荷輸送層塗工液〕
化合物ＮＯ．２−９６の化合物 ４部
化合物ＮＯ．１−８１の化合物 ４部
ポリカーボネート樹脂
（三菱瓦斯化学社製：ユーピロン Ｚ−３００） １０部
塩化メチレン ５０部
１，２−ジクロロエタン ３５部
比較例３
実施例３の電荷輸送層塗工液を下記組成のものにした以外は実施例３と同様にして比較例の電子写真感光体を作製した。
〔電荷輸送層塗工液〕
化合物ＮＯ．２−９６の化合物 ８部
ポリカーボネート樹脂
（三菱瓦斯化学社製：ユーピロン Ｚ−３００） １０部
塩化メチレン ５０部
１，２−ジクロロエタン ３５部
実施例４
アルミニウムシリンダー上に下記組成の感光層塗工液を塗布・乾燥し、厚さ２６μｍの単層感光層を形成し、本発明の電子写真感光体を作製した。
下記構造式の電荷発生材料 ３部

1 part of polyester (Toyobo Co., Ltd .: Byron 200)
150 parts of cyclohexanone
100 parts of cyclohexane
[Charge transport layer coating solution]
Compound NO. 2-96 compounds 4 parts
Compound NO. 1-81 compounds 4 parts
Polycarbonate resin
(Mitsubishi Gas Chemical Co., Ltd .: Iupilon Z-300) 10 parts
50 parts of methylene chloride
1,2-dichloroethane 35 parts Comparative Example 3
A comparative electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the charge transport layer coating solution of Example 3 had the following composition.
[Charge transport layer coating solution]
Compound NO. 2-96 compounds 8 parts
Polycarbonate resin
(Mitsubishi Gas Chemical Co., Ltd .: Iupilon Z-300) 10 parts
50 parts of methylene chloride
1,2-dichloroethane 35 parts Example 4
A photosensitive layer coating solution having the following composition was applied onto an aluminum cylinder and dried to form a single-layer photosensitive layer having a thickness of 26 μm, thereby producing the electrophotographic photosensitive member of the present invention.
3 parts of charge generation material of the following structural formula

ポリカーボネート
（帝人化成社製：パンライトＫ−１３００） ２１部
化合物ＮＯ．２−２１の化合物 ８部
化合物ＮＯ．１−３の化合物 １０部
テトラヒドラフラン ２００部
比較例４
アルミニウムシリンダー上に下記組成の感光層塗工液を塗布・乾燥し、厚さ２３μｍの単層感光層を形成し、比較例の電子写真感光体を作製した。
〔感光層塗工液〕
実施例４と同じ電荷発生材料 ３部
ポリカーボネート
（帝人化成社製、パンライトＫ−１３００） ２１部
化合物ＮＯ．２−２１の化合物 １８部
テトラヒドロフラン ２００部
以上の実施例１〜４および比較例１〜４の各感光体を特開昭６０−１００１６７号公報に開示されている評価装置を用いて次のような測定を行なった。コロナ放電電圧−６．０ｋＶ（または＋５．６ｋＶ）で帯電２０秒後の電位Ｖｍ（Ｖ）、暗減衰２０秒後の電位Ｖｏ（Ｖ）、強度６ｌｕｘの白色光による露光２０秒後の残留電位ＶＲ（Ｖ）、更に電位Ｖｏを１／２に減衰させるのに必要な露光量Ｅ1/2［ｌｕｘ・ｓｅｃ］を測定した。電位保持率＝Ｖｏ／Ｖｍと定義する。また、各感光体をリコー製複写機ＦＴ−３３００（ないしは感光体を正帯電できるように改造したもの）に搭載して連続３万枚の複写を行い、異常画像の有無を目視により判定した。また、複写試験終了後の各感光体は、上記と同じ方法で感光体特性を測定した。試験結果を表４０に示す。

Polycarbonate
(Teijin Chemicals: Panlite K-1300) 21 parts
Compound NO. 2-21 compounds 8 parts
Compound NO. 1-3 parts of compound 10 parts
Tetrahydrafuran 200 parts Comparative Example 4
A photosensitive layer coating solution having the following composition was applied on an aluminum cylinder and dried to form a single-layer photosensitive layer having a thickness of 23 μm, thereby preparing a comparative electrophotographic photosensitive member.
[Photosensitive layer coating solution]
3 parts of the same charge generating material as in Example 4
Polycarbonate
(Teijin Chemicals, Panlite K-1300) 21 parts
Compound NO. 18 parts of 2-21 compound
Tetrahydrofuran 200 parts Each of the photoreceptors of Examples 1 to 4 and Comparative Examples 1 to 4 described above was subjected to the following measurements using an evaluation apparatus disclosed in JP-A-60-1000016. Potential Vm (V) after 20 seconds of charging at a corona discharge voltage of -6.0 kV (or +5.6 kV), potential Vo (V) after 20 seconds of dark decay, and residual potential after 20 seconds of exposure with white light having an intensity of 6 lux The exposure amount E1 / 2 [lux · sec] required to attenuate VR (V) and further the potential Vo to 1/2 was measured. The potential holding ratio is defined as Vo / Vm. Each photoconductor was mounted on a Ricoh copier FT-3300 (or the photoconductor was modified so that it could be positively charged), and 30,000 continuous copies were made, and the presence or absence of an abnormal image was visually determined. Each photoconductor after the copying test was measured for the photoconductor characteristics by the same method as described above. The test results are shown in Table 40.

次に電荷輸送材料として一般式（１）および一般式（３）で示される化合物を併用した場合について、実施例５から８および比較例５から８により説明する。

Next, the case where the compounds represented by the general formula (1) and the general formula (3) are used in combination as the charge transport material will be described with reference to Examples 5 to 8 and Comparative Examples 5 to 8.

Example 5
An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 1 except that the charge transport layer coating solution of Example 1 had the following composition.
[Charge transport layer coating solution]
Compound NO. 3-25 compounds 3 parts
Compound NO. 1-3 parts of compound 6 parts
10 parts of polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite K-1300)
Tetrahydrofuran 75 parts Comparative Example 5
A comparative electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the charge transport layer coating solution of Example 5 had the following composition.
[Charge transport layer coating solution]
Compound NO. 9-25 compounds 9 parts
10 parts of polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite K-1300)
Tetrahydrofuran 75 parts Example 6
An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 2 except that the charge transport layer coating solution of Example 2 had the following composition.
[Charge transport layer coating solution]
Compound NO. 2-146 compounds 2 parts
Compound NO. 1-48 compound 8 parts
10 parts of polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite K-1300)
80 parts of methylene chloride Comparative Example 6
In the charge transport layer coating solution of Example 6, compound NO. A comparative electrophotographic photosensitive member was produced in the same manner as in Example 6 except that the compound of 3-146 was not added.

Example 7
An electrophotographic photosensitive member of the present invention was produced in the same manner as in Example 3 except that the charge transport layer coating solution of Example 3 was changed to one having the following composition.
[Charge transport layer coating solution]
Compound NO. 3-256 compounds 4 parts
Compound NO. 1-81 compounds 4 parts
10 parts of polycarbonate (Mitsubishi Gas Chemical Co., Ltd .: Iupilon Z-300)
50 parts of methylene chloride
1,2-dichloroethane 35 parts Comparative Example 7
A comparative electrophotographic photosensitive member was produced in the same manner as in Example 7 except that the charge transport layer coating solution of Example 7 was changed to the one having the following composition.
[Charge transport layer coating solution]
Compound NO. 3-256 compounds 8 parts
10 parts of polycarbonate (Mitsubishi Gas Chemical Co., Ltd .: Iupilon Z-300)
50 parts of methylene chloride
1,2-dichloroethane 35 parts Example 8
On the aluminum cylinder, a photosensitive layer coating solution having the following composition was applied and dried to form a single-layer photosensitive layer having a thickness of 23 μm to produce the electrophotographic photosensitive member of the present invention.
[Photosensitive layer coating solution]
3 parts of the same charge generating material as in Example 4
21 parts of polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite K-1300)
Compound NO. 3-25 compounds 8 parts
Compound NO. 1-3 parts of compound 10 parts
Tetrahydrofuran 200 parts Comparative Example 8
A photosensitive layer coating solution having the following composition was applied onto an aluminum cylinder and dried to form a single-layer photosensitive layer having a thickness of 23 μm, thereby preparing a comparative electrophotographic photosensitive member.
[Photosensitive layer coating solution]
3 parts of the same charge generating material as in Example 4
21 parts of polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite K-1300)
Compound NO. 18 parts of 3-25 compounds
Tetrahydrofuran 200 parts Photoreceptor characteristics of each of the photoreceptors of Examples 5 to 8 and Comparative Examples 5 to 8 were measured in the same manner as described above. The test results are shown in Table 41.

次に電荷輸送材料として一般式（１）で示される化合物と一般式（４）で示される化合物を併用した場合について、実施例９から１２および比較例９から１２により説明する。

Next, examples in which the compound represented by the general formula (1) and the compound represented by the general formula (4) are used in combination as the charge transport material will be described with reference to Examples 9 to 12 and Comparative Examples 9 to 12.

Example 9
The electrophotographic photosensitive member of the present invention was prepared in the same manner as in Example 1 except that the charge transport layer coating solution of Example 1 was changed to the following composition.
[Charge transport layer coating solution]
Compound NO. 4-20 compounds 3 parts
Compound NO. 1-3 parts of compound 6 parts
10 parts of polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite K-1300)
Tetrahydrofuran 75 parts Comparative Example 9
A comparative electrophotographic photosensitive member was produced in the same manner as in Example 9 except that the charge transport layer coating solution in Example 9 was changed to the one having the following composition.
[Charge transport layer coating solution]
Compound NO. 9 parts of 4-20 compounds
Polycarbonate
(Teijin Chemicals: Panlite K-1300) 10 parts
Tetrahydrofuran 75 parts Example 10
An electrophotographic photosensitive member of the present invention was produced in the same manner as in Example 2 except that the charge transport layer coating solution of Example 2 was changed to one having the following composition.
[Charge transport layer coating solution]
Compound NO. 4-29 compounds 2 parts
Compound NO. 1-48 compound 8 parts
Polycarbonate
(Teijin Chemicals: Panlite L-1250) 10 parts
80 parts of methylene chloride Comparative Example 10
In the charge transport layer coating solution of Example 10, compound NO. A comparative electrophotographic photosensitive member was produced in the same manner as in Example 10 except that the compound 4-29 was not added.

Example 11
An electrophotographic photosensitive member of the present invention was produced in the same manner as in Example 3 except that the charge transport layer coating solution of Example 3 was changed to one having the following composition.
[Charge transport layer coating solution]
Compound NO4-73 Compound 4 parts
Compound NO. 1-81 compounds 4 parts
Polycarbonate resin
(Mitsubishi Gas Chemical Co., Ltd .: Iupilon Z-300) 10 parts
50 parts of methylene chloride
1,2-dichloroethane 35 parts Comparative Example 11
A comparative electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the charge transport layer coating solution of Example 11 was changed to the following composition.
[Charge transport layer coating solution]
Compound NO. 4-73 compounds 8 parts
Polycarbonate resin
(Mitsubishi Gas Chemical Co., Ltd .: Iupilon Z-300) 10 parts
50 parts of methylene chloride
1,2-dichloroethane 35 parts Example 12
A photosensitive layer coating solution having the following composition was applied on an aluminum cylinder and dried to form a single-layer photosensitive layer having a thickness of 23 μm, thereby producing the electrophotographic photosensitive member of the present invention.
[Photosensitive layer coating solution]
3 parts of the same charge generating material as in Example 4
Polycarbonate
(Teijin Chemicals: Panlite K-1300) 21 parts
Compound NO. 4-20 compounds 8 parts
Compound NO. 1-3 parts of compound 10 parts
Tetrahydrofuran 200 parts Comparative Example 12
A photosensitive layer coating solution having the following composition was applied on an aluminum cylinder and dried to form a single-layer photosensitive layer having a thickness of 23 μm, thereby preparing a comparative electrophotographic photosensitive member.
[Photosensitive layer coating solution]
3 parts of the same charge generating material as in Example 4
Polycarbonate
(Teijin Chemicals: Panlite K-1300) 21 parts
Compound NO. 4-20 compounds 18 parts
Tetrahydrofuran 200 parts Photoreceptor characteristics of each of the photoreceptors of Examples 9 to 12 and Comparative Examples 9 to 12 were measured in the same manner as described above. The test results are shown in Table 42.

比較例１３
実施例１の電荷輸送層に用いた化合物ＮＯ．２−２１を下記化合物に変えた以外は実施例１と同様にして比較例の電子写真感光体を作製した。

Comparative Example 13
Compound NO. 1 used in the charge transport layer of Example 1 A comparative electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 2-21 was changed to the following compound.

比較例１４
実施例３の電荷輸送層に用いた化合物ＮＯ．２−９６の化合物を下記化合物に変えた以外は実施例３と同様にして比較例１４の電子写真感光体を作製した。

Comparative Example 14
The compound NO. 1 used in the charge transport layer of Example 3 was used. An electrophotographic photoreceptor of Comparative Example 14 was produced in the same manner as in Example 3 except that the compound 2-96 was changed to the following compound.

上記比較例１３〜１４の試験結果を表４３に示す。

Table 43 shows the test results of Comparative Examples 13 to 14.

It is sectional drawing of a single layer photoreceptor. It is sectional drawing which shows the structural example of a laminated photoconductor. It is sectional drawing which shows the structural example of a laminated photoconductor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Conductive support body 15 Single layer photosensitive layer 17 Charge generation layer 19 Charge transport layer

Claims (6)

A charge generation layer mainly composed of a charge generation material, a compound represented by the following general formula (1), and a charge transport layer containing a compound represented by the following general formula (4) are laminated on a conductive support. An electrophotographic photosensitive member characterized by the above.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group, Ar ₁ is a substituted or unsubstituted aryl group, Ar ₂ represents a substituted or unsubstituted arylene group. Ar ₁ and R ₁ may form a ring together, and n is an integer of 0 or 1.

In the formula, R ₁ and R ₂ are a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a substituted or unsubstituted alkyl group, and R ₃ and R ₄ are a hydrogen atom, a cyano group, an alkoxycarbonyl group, or a substituted or unsubstituted group. A substituted alkyl group, R ₅ represents a hydrogen atom, a lower alkyl group or an alkoxy group . j represents 1 to 5, k represents 1 to 4, l represents 0 to 2, m represents 1 or 2, and n represents an integer of 1 to 3. W is a hydrogen atom or a structural formula when m is 1

And when m is 2, the structural formula

It is a functional group shown by.   2. The electrophotographic photosensitive member according to claim 1, wherein an undercoat layer, the charge generation layer, and the charge transport layer are laminated on the conductive support. 3. The electrophotographic photosensitive member according to claim 1, wherein the conductive support is an aluminum support. Electrons characterized in that a single-layer photosensitive layer containing at least a charge generating material, a compound represented by the following general formula (1) and a compound represented by the following general formula (4) is provided on a conductive support. Photoconductor.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group, Ar ₁ is a substituted or unsubstituted aryl group, Ar ₂ represents a substituted or unsubstituted arylene group. Ar ₁ and R ₁ may form a ring together, and n is an integer of 0 or 1.

In the formula, R ₁ and R ₂ are a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a substituted or unsubstituted alkyl group, and R ₃ and R ₄ are a hydrogen atom, a cyano group, an alkoxycarbonyl group, or a substituted or unsubstituted group. A substituted alkyl group, R ₅ represents a hydrogen atom, a lower alkyl group or an alkoxy group . j is 1 to 5, k is 1 to 4, l is 0 to 2, m represents an integer of 1 or 2, n is 1-3. W is a hydrogen atom or a structural formula when m is 1

And when m is 2, the structural formula

It is a functional group shown by. Wherein on a conductive support, an undercoat layer, an electrophotographic photosensitive member according to claim 4, before Kitanso photosensitive layer is characterized in that it is laminated. The electrophotographic photosensitive member according to claim 4 or 5, wherein the conductive support is an aluminum support.

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