JP5168478B2 - Electrophotographic photosensitive member, electrophotographic method, electrophotographic apparatus, and process cartridge for electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member containing at least one specific naphthalenetetracarboxylic acid diimide derivative in a photosensitive layer, and an electrophotographic method, an electrophotographic apparatus, and an electrophotographic method using the electrophotographic photosensitive member. It relates to a process cartridge.

  In recent years, there has been a remarkable development in information processing system machines using electrophotography. In particular, laser printers and digital copying machines that convert information into digital signals and record information using light have significantly improved print quality and reliability. Furthermore, they have been applied to laser printers or digital copiers capable of full-color printing by fusing with high-speed technology. From such a background, it is particularly important to achieve both high image quality and high durability as a required photoreceptor function.

  As photoconductors used in these electrophotographic laser printers, digital copiers, etc., those using organic photosensitive materials (OPC) are generally widely used for reasons such as cost, productivity and non-pollution. Applied. The layer structure of the OPC photoreceptor is roughly divided into a single layer type and a function separation type laminated structure. The first practical OPC, the PVK-TNF charge transfer complex type photoreceptor, was the former single layer type.

  On the other hand, in 1968, Hayashi and Regensburger independently invented a PVK / a-Se laminated photoreceptor, and later in 1977 by Melz et al. And in 1978 Schlosser called an organic pigment dispersion layer and an organic low molecular weight dispersion polymer layer. A multi-layer photoconductor in which all photosensitive layers are made of organic materials has been announced. These are functionally separated from the concept of a charge generation layer (CGL) that absorbs light and generates charges, and a charge transport layer (CTL) that injects and transports charges generated by CGL and neutralizes surface charges. Also called a mold-laminated photoconductor.

  However, organic photoconductors have larger film scraping due to repeated use than inorganic ones. If the photoconductive layer is further scraped off, the surface of the photoconductor is deteriorated due to a decrease in charge potential, photosensitivity, or scratches on the surface of the photoconductor. There is a strong tendency to promote dirt, image density reduction or image quality degradation. Therefore, the wear resistance of organic photoreceptors has been cited as a major problem. Further, in recent years, with the increase in the speed of an electrophotographic apparatus or the reduction in the diameter of the photoreceptor accompanying the downsizing of the apparatus, it has become a more important issue to improve the durability of the photoreceptor.

  As a method for improving the abrasion resistance of the photoconductor, a method for imparting lubricity to the photosensitive layer, curing it, or containing a filler, or a low molecular charge transport material (CTM) molecular dispersed polymer layer can be used. Methods using polymer charge transport materials are widely known. However, a new problem arises when the abrasion of the photosensitive layer is suppressed by these methods. That is, ozone, NOx, and other oxidizing substances that are repeatedly used on the surface of the photosensitive layer and adsorbed by the surrounding environment are adsorbed. Depending on the repeated use and use environment, the resistance of the outermost surface is lowered, and image flow (image blur), etc. Known to cause problems. Conventionally, the problem has been avoided to some extent by removing the blur generating material little by little together with the photosensitive layer.

  However, as described above, in order to meet the recent demand for higher resolution and higher durability, a new method has to be provided. One method of reducing these effects is to mount a heater on the photoreceptor, which is a major obstacle to downsizing the apparatus and reducing power consumption. Additives such as antioxidants are also effective means, but mere additives are those that do not have photoconductivity. Therefore, addition of a large amount to the photosensitive layer can reduce the sensitivity and increase the residual potential. It will imitate the problem of photographic characteristics.

  As described above, electrophotographic photoreceptors that have high wear resistance or have less shaving due to process design around the photoreceptor can avoid adverse effects on image quality such as image blurring and reduced resolution as side effects. Therefore, it has been difficult to achieve both high durability and high image quality. This is because a higher resistance is suitable for suppressing the occurrence of image blur, and a lower resistance is suitable for suppressing the increase in residual potential. It is difficult to solve.

  Most of the electrophotographic photoreceptors in practical use are function-separated type electrophotographic photoreceptors in which a charge generation layer and a charge transport layer are laminated on a conductive substrate. As a charge transport material contained in the charge transport layer, A hole transport material is used. These are used exclusively for negatively charged electrophotographic processes.

  In addition, a highly reliable charging method in the electrophotographic process is based on corona discharge, and this method is adopted in most copying machines and printers. However, as is well known, the negative corona discharge is unstable compared to the positive polarity, and for this reason, a scorotron charging method is adopted, which is a factor in increasing costs. The negative corona discharge is accompanied by a larger amount of ozone, a substance that causes chemical damage. Therefore, it is generated during the long-term oxidative degradation of the binder resin and charge transfer material due to ozone generated during charging, and is generated during charging. As a result, accumulation of ionic compounds such as nitrogen oxide ions, sulfur oxide ions, ammonium ions, etc. on the surface of the photoconductor causes a problem of image quality degradation. For this reason, ozone filters are often used in negatively charged copying machines and printers in order to prevent ozone from being discharged to the outside, which also increases the cost of the apparatus. Also, a large amount of ozone is a problem of environmental pollution.

  In order to solve these problems, development of a positively charged electrophotographic photosensitive member is underway. If the positive charging method is used, the generation amount of ozone, nitrogen oxide ions, etc. is suppressed, and the use of a two-component developer that is widely used at present makes the electrophotographic photosensitive member positively charged. A stable image with little environmental fluctuation can be obtained. From this aspect, a positively charged electrophotographic photosensitive member is desirable.

  However, positively charged single-layer and reverse-layer photoconductors have a charge generating material that is very sensitive to oxidizing substances such as ozone and nitrogen oxide ions in the vicinity of the surface. For example, there is a drawback that the characteristic fluctuation due to the exhaust gas from the oil fan heater or the car is large.

  On the other hand, in the case of a high-speed copying process, it is preferable to use a negative charging type rather than a positive charging type as described above. The reason for this is that organic materials exhibiting high charge mobility that does not interfere with high-speed copying processes are currently limited to hole transport materials that have only the property of hole transfer, and are therefore correct. This is because, in a forward layered electrophotographic photosensitive member in which a charge transporting layer formed using a hole transporting material is arranged on the surface side, the charging property is limited to negative charging on the principle of operation.

  As described above, regarding the charging polarity, if the electrophotographic photosensitive member can be used in both positive and negative polarities, the application range of the photosensitive member can be further expanded, and the cost can be reduced by reducing the number of photosensitive members. This is advantageous for speeding up.

  From such a situation, an electrophotographic photosensitive member capable of being charged in both polarities is disclosed in Japanese Patent No. 2732697 (Patent Document 1), but the diphenoquinone derivative of the electron transport material used here has a slight charge mobility. Since it is low, the photoconductor sensitivity characteristics are not sufficient when considering high speed and downsizing of copying machines and printers, and further, there is a disadvantage that image blur is caused by repeated use.

  Japanese Unexamined Patent Publication No. 2000-231204 (Patent Document 2) discloses an aromatic compound having a dialkylamino group as an acid scavenger to a photoreceptor. This compound is effective for image quality after repeated use. However, since the charge transport ability is low, it is difficult to meet demands for high sensitivity and high speed, and there is a limit in the amount of addition.

  Furthermore, stilbene compounds having a dialkylamino group disclosed in JP-A-60-196768 (Patent Document 3), Japanese Patent No. 2884353 (Patent Document 4) and the like are also effective against image blur caused by an oxidation-resistant gas. Effectiveness is described in [Itami et al., Konica Technical Report, Vol. 13, p. 37, 2000].

  However, since this has a dialkylamino group that is a substituent of a strong mesomeric effect (+ M effect) at the resonance site of the triarylamine structure that is a charge transport site, the overall ionization potential value becomes abnormally small. Therefore, the charge retention ability of the photosensitive layer used alone as a hole transporting material is remarkably deteriorated from the beginning or by repeated use. Even when mixed with substances, the ionization potential values of the above stilbene compounds are much smaller than those, so the stilbene compounds become hole trap sites for mobile charges, resulting in an electrophotographic photosensitive member with significantly low sensitivity and a large residual potential. End up.

Japanese Patent Application Laid-Open No. 2004-258253 (Patent Document 5) proposes a photoconductor that includes a stilbene compound and a specific diamine compound and has improved environmental resistance against repeated use and acidic gas without causing a decrease in sensitivity. Has been.
However, it is still not sufficient to realize downsizing of the apparatus accompanying high-speed printing or reduction in the diameter of the photoreceptor.

  Further, it is disclosed that naphthalenetetracarboxylic acid diimide derivatives themselves are used as acceptors for forming a charge transfer complex (Patent Document 6) and also used as compounds having an anti-helicobacter action (Pharmaceuticals) (Patent Document 7). However, it is not suggested to be used for an electrophotographic photoreceptor.

Japanese Patent No. 2732697 JP 2000-231204 A JP-A-60-196768 Japanese Patent No. 2884353 JP 2004-258253 A DE 1230031 WO2002040479

  An object of the present invention is to provide an electrophotographic photosensitive material that has high durability even for repeated use over a long period of time, suppresses image deterioration due to image density reduction or image blurring, and stably obtains high-quality images. To provide a body. In addition, photoconductors that can handle bipolar charging are obtained, and by using these photoconductors, it is not necessary to replace the photoconductors, and it is possible to reduce the size of the apparatus due to high-speed printing or reduction in the diameter of the photoconductor. Another object of the present invention is to provide an electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge capable of stably obtaining a high-quality image even in repeated use.

  The above-described problem is (1) “an electrophotographic photosensitive member provided with at least a photosensitive layer on a conductive support, wherein the photosensitive layer is a naphthalenetetracarboxylic acid represented by the following general formula (1): An electrophotographic photoreceptor comprising a diimide derivative;

［式中、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ は置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表し、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ は、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表し、それぞれ同一でも異なっていてもよい。ただし、Ｒ ¹ とＲ ² は互いに結合していない。Ｒ ³ とＲ ⁴ も互いに結合していない。］」、
（２）「前記感光層は、少なくとも電荷発生層、電荷輸送層を順次積層したものであることを特徴とする前記第（１）項記載の電子写真感光体」、
（３）「前記感光層は、少なくとも電荷輸送層、電荷発生層を順次積層したものであることを特徴とする前記第（１）項記載の電子写真感光体」、
（４）「前記感光層は、単層型の感光層であることを特徴とする前記第（１）項記載の電子写真感光体」、
（５）「前記感光層は、電荷輸送物質をさらに含むものであることを特徴とする前記第（１）項乃至第（４）項記載の電子写真感光体」、
（６）「前記電荷輸送物質が下記一般式（２）で表されるスチルベン誘導体であることを特徴とする前記第（５）項記載の電子写真感光体；

[Wherein R ¹ , R ² , R ³ , R ⁴ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, R ⁵ , R ⁶ , R ⁷ , R ⁸ are A hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group may be the same or different. However, R ¹ and R ² are not bonded to each other. R ³ and R ⁴ are not bonded to each other . ] ",
(2) "The electrophotographic photosensitive member according to (1) above, wherein the photosensitive layer is a laminate in which at least a charge generation layer and a charge transport layer are sequentially laminated",
(3) "The electrophotographic photosensitive member according to (1) above, wherein the photosensitive layer is a laminate in which at least a charge transport layer and a charge generation layer are sequentially laminated",
(4) "The electrophotographic photosensitive member according to item (1), wherein the photosensitive layer is a single layer type photosensitive layer",
(5) "The electrophotographic photosensitive member according to any one of (1) to (4) above, wherein the photosensitive layer further contains a charge transport material",
(6) “The electrophotographic photosensitive member according to (5) above, wherein the charge transporting substance is a stilbene derivative represented by the following general formula (2);

［式中、Ｘは単結合もしくはビニレン基を表し、Ｒ ¹ は水素原子、置換もしくは無置換のアルキル基または置換もしくは無置換の芳香族炭化水素基を表し、Ａｒ ¹ は置換もしくは無置換の芳香族炭化水素基を表し、Ｒ ⁵ は置換もしくは無置換のアルキル基、あるいは置換もしくは無置換の芳香族炭化水素基を表し、Ａｒ ¹ とＲ ⁵ は共同で環を形成しても良い。Ａは一般式（３）、一般式（４）、９−アントリル基または置換もしくは無置換のカルバゾリル基を表す。

[Wherein, X represents a single bond or a vinylene group, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ represents a substituted or unsubstituted aromatic group. Represents a hydrocarbon group, R ⁵ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ and R ⁵ may form a ring together. A represents General formula (3), General formula (4), 9-anthryl group, or a substituted or unsubstituted carbazolyl group.

ここでＲ ² は水素原子、アルキル基、アルコキシ基、ハロゲン原子または一般式（５）を表し、ｍは１〜３の整数を表し、２以上の時Ｒ ² は同一でも異なっても良い

Here, R ² represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or general formula (5), m represents an integer of 1 to 3, and when 2 or more, R ² may be the same or different.

（ただし、Ｒ ³ およびＲ ⁴ は置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を示し、Ｒ ³ およびＲ ⁴ は同じでも異なっていてもよく、環を形成しても良い）。］」、
（７）「前記電荷輸送物質が下記一般式（６）で表されるアミノビフェニル誘導体であることを特徴とする前記第（５）項記載の電子写真感光体；

(However, R ³ and R ⁴ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and R ³ and R ⁴ may be the same or different and may form a ring. good). ] ",
(7) “The electrophotographic photosensitive member according to (5) above, wherein the charge transporting substance is an aminobiphenyl derivative represented by the following general formula (6);

［式中、Ｒ ¹ 、Ｒ ³ およびＲ ⁴ は水素原子、アミノ基、アルコキシ基、チオアルコキシ基、アリールオキシ基、メチレンジオキシ基、置換もしくは無置換のアルキル基、ハロゲン原子または置換もしくは無置換の芳香族炭化水素基を、Ｒ ² は水素原子、アルコキシ基、置換もしくは無置換のアルキル基またはハロゲン原子を表す。また、ｋ，ｌ，ｍおよびｎは１、２、３または４の整数であり、それぞれが２、３または４の整数の時は、前記Ｒ ¹ 、Ｒ ² 、Ｒ ³ およびＲ ⁴ は同じでも異なっていても良い。］」、
（８）「前記電荷輸送物質が下記一般式（７）で表されるジスチルベン誘導体であることを特徴とする前記第（５）項記載の電子写真感光体；

[Wherein R ¹ , R ³ and R ⁴ are a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom or a substituted or unsubstituted group. R ² represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group or a halogen atom. K, l, m and n are integers of ¹ , ² , 3 or 4, and when each is an integer of 2, 3 or 4, R ¹ , R ² , R ³ and R ⁴ may be the same. It may be different. ] ",
(8) The electrophotographic photosensitive member according to (5), wherein the charge transporting substance is a distilbene derivative represented by the following general formula (7);

［式中、Ｘは単結合もしくはビニレン基を表し、 Ｒ ¹ は水素原子、置換もしくは無置換のアルキル基または置換もしくは無置換の芳香族炭化水素基を表し、Ａｒ ¹ は置換もしくは無置換の芳香族炭化水素基を表し、Ｒ ³ は置換もしくは無置換のアルキル基、あるいは置換もしくは無置換の芳香族炭化水素基を表し、Ａｒ ¹ とＲ ³ は共同で環を形成しても良い。またＲ ⁴ は置換もしくは無置換のアルキル基または置換もしくは無置換の芳香族炭化水素基を表す。Ａｒ ² は下記一般式（８）または一般式（９）を表す。

[Wherein, X represents a single bond or a vinylene group, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ represents a substituted or unsubstituted aromatic group. Represents a hydrocarbon group, R ³ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ and R ³ may form a ring together. R ⁴ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. Ar ² represents the following general formula (8) or general formula (9).

ここでＲ ² は水素原子、アルキル基、アルコキシ基、ハロゲン原子を表し、ｍは１〜３の整数を表し、２以上の時Ｒ ² は同一でも異なっても良い。］」、
（９）「前記電荷輸送物質が下記一般式（１０）で表されるジビニル誘導体であることを特徴とする前記第（５）項記載の電子写真感光体；

Here, R ² represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 1 to 3, and R ² may be the same or different when 2 or more. ] ",
(9) “The electrophotographic photosensitive member according to (5), wherein the charge transporting substance is a divinyl derivative represented by the following general formula (10);

［式中、Ｘは単結合もしくはビニレン基を表し、 Ｒ ¹ は水素原子、置換もしくは無置換のアルキル基または置換もしくは無置換の芳香族炭化水素基を表し、Ａｒ ¹ は置換もしくは無置換の２価の芳香族炭化水素基を表し、Ｒ ⁵ は置換もしくは無置換のアルキル基、あるいは置換もしくは無置換の芳香族炭化水素基を表し、Ａは一般式（３）、一般式（４）、９−アントリル基または置換もしくは無置換のカルバゾリル基を表す。

[Wherein, X represents a single bond or a vinylene group, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ represents a substituted or unsubstituted 2 group. R ⁵ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and A represents a general formula (3), a general formula (4), 9 -Represents an anthryl group or a substituted or unsubstituted carbazolyl group.

ここでＲ ² は水素原子、アルキル基、アルコキシ基、ハロゲン原子または一般式（５）を表す。ｍは１〜３の整数を表し、２以上の時Ｒ ² は同一でも異なっても良い

Here, R ² represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or general formula (5). m represents an integer of 1 to 3, and when 2 or more, R ² may be the same or different.

（ただし、Ｒ ³ およびＲ ⁴ は置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を示し、Ｒ ³ およびＲ ⁴ は同じでも異なっていてもよく、環を形成しても良い）。］」、
（１０）「電子写真感光体に、少なくとも帯電、画像露光、現像、転写が繰り返し行われる電子写真方法であって、該電子写真感光体は前記第（１）項乃至第（９）項記載の電子写真感光体であることを特徴とする電子写真方法」、
（１１）「電子写真感光体に、少なくとも帯電、画像露光、現像、転写を繰り返し行い、かつ画像露光の際にはＬＤあるいはＬＥＤ等によって感光体上に静電潜像の書き込みが行われる、デジタル方式の電子写真方法であって、該電子写真感光体は前記第（１）項乃至第（９）項記載の電子写真感光体であることを特徴とする電子写真方法」、
（１２）「少なくとも帯電手段、画像露光手段、現像手段、転写手段および電子写真感光体を具備してなる電子写真装置であって、該電子写真感光体は前記第（１）項乃至第（９）項記載の電子写真感光体であることを特徴とする電子写真装置」、
（１３）「少なくとも帯電手段、画像露光手段、現像手段、転写手段および電子写真感光体を具備してなる電子写真装置であって、画像露光手段にＬＤあるいはＬＥＤ等を使用することによって感光体上に静電潜像の書き込みが行われる、デジタル方式の電子写真装置であって、該電子写真感光体は前記第（１）項乃至第（９）項記載の電子写真感光体であることを特徴とする電子写真装置」、
（１４）「少なくとも電子写真感光体を具備してなる電子写真装置用プロセスカートリッジであって、該電子写真感光体は前記第（１）項乃至第（９）項記載の電子写真感光体であることを特徴とする電子写真装置用プロセスカートリッジ」により解決される。

(However, R ³ and R ⁴ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and R ³ and R ⁴ may be the same or different and may form a ring. good). ] ",
(10) “An electrophotographic method in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is described in (1) to (9)” above. An electrophotographic method characterized by being an electrophotographic photoreceptor ",
(11) A digital image in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, and an electrostatic latent image is written on the photosensitive member by an LD or LED during image exposure. An electrophotographic method, wherein the electrophotographic photosensitive member is an electrophotographic photosensitive member according to any one of (1) to (9),
(12) “An electrophotographic apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the items (1) to (9). An electrophotographic photosensitive member characterized by being an electrophotographic photosensitive member according to the item),
(13) “An electrophotographic apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means, and an electrophotographic photosensitive member, wherein an LD or LED is used as the image exposing means on the photosensitive member. A digital electrophotographic apparatus in which an electrostatic latent image is written, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of (1) to (9). Electrophotographic device "
(14) “A process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of the items (1) to (9). This is solved by a process cartridge for an electrophotographic apparatus.

  According to the present invention, by including the naphthalene tetracarboxylic acid diimide derivative represented by the general formula (1), the environmental resistance to repeated use, oxidizing gas, and the like is greatly improved without causing a decrease in sensitivity. Therefore, it is possible to obtain a photoconductor having high durability and capable of obtaining high resolution image quality over a long period of time. According to the present invention, it is possible to achieve both high durability and high image quality of an electrophotographic photosensitive member, a high-quality image can be stably obtained over a long period of time, and furthermore, an electrophotographic photosensitive member that can handle bipolar charging, and An electrophotographic method, an electrophotographic apparatus, and a process cartridge for an electrophotographic apparatus using the same are provided.

  As a result of investigations, the present inventors have incorporated at least one naphthalenetetracarboxylic acid diimide derivative represented by the following general formula (1) into the photosensitive layer, whereby the above-described blur generating substance such as an oxidizing gas is used. It has been found that a photoconductor capable of solving problems such as image blur (image flow) and the like and capable of dealing with bipolar charging can be obtained.

［式中、Ｒ ¹ 、Ｒ ² とＲ ³ 、Ｒ ⁴ は置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表し、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ は、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表し、それぞれ同一でも異なっていてもよい。ただし、Ｒ ¹ とＲ ² は互いに結合していない。Ｒ ³ とＲ ⁴ も互いに結合していない］

[Wherein R ¹ , R ² and R ³ , R ⁴ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, R ⁵ , R ⁶ , R ⁷ , R ⁸ are A hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group may be the same or different. However, R ¹ and R ² are not bonded to each other. R ³ and R ⁴ are also not bonded to each other ]

The reason why the naphthalenetetracarboxylic acid diimide derivative in the present invention is effective for maintaining the image quality by repeated use is not clear at present, but the amino group contained in the chemical structure is a strongly basic group. An electrical neutralizing effect on the oxidizing gas that is considered to be a causative substance for image blurring is estimated.
In addition, the naphthalene tetracarboxylic acid diimide derivative in the present invention has higher sensitivity, repeat stability and the like when used in combination with other charge transport materials.

In addition, since the naphthalene tetracarboxylic acid diimide derivative in the present invention is an electron transporting substance, a photoreceptor using the naphthalene tetracarboxylic acid diimide derivative can be used for bipolar charging by mixing with a kind of layer structure and a hole transporting substance. You can also get a body.
Therefore, by satisfying the following constituent requirements, it is possible to achieve both high durability and high image quality, and an electrophotographic photosensitive member capable of bipolar charging that can stably obtain high-quality images even after repeated use. In addition, an electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge capable of stably obtaining a high-quality image even in repeated use have been provided.

  Hereinafter, the electrophotographic photosensitive member of the present invention, the electrophotographic method using the same, the electrophotographic apparatus, and the electrophotographic process cartridge will be described in detail.

  First, the details of the naphthalene tetracarboxylic acid diimide derivative represented by the following general formula (1) to be contained in the photosensitive layer in the present invention will be described.

［式中、Ｒ ¹ 、Ｒ ² とＲ ³ 、Ｒ ⁴ は置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表し、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ は、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表し、それぞれ同一でも異なっていてもよい。ただし、Ｒ ¹ とＲ ² は互いに結合していない。Ｒ ³ とＲ ⁴ も互いに結合していない。］

[Wherein R ¹ , R ² and R ³ , R ⁴ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, R ⁵ , R ⁶ , R ⁷ , R ⁸ are A hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group may be the same or different. However, R ¹ and R ² are not bonded to each other. R ³ and R ⁴ are not bonded to each other . ]

  As a method for producing the naphthalenetetracarboxylic acid diimide derivative represented by the general formula (1), a naphthalene-1,4,5,8-tetracarboxylic dianhydride derivative is converted to a 1,1-disubstituted hydrazine derivative. Is reacted in the absence of a solvent or in the presence of a solvent. The solvent is not particularly limited, and examples thereof include benzene, toluene, xylene, chloronaphthalene, acetic acid, pyridine, methylpyridine, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylethyleneurea, dimethylsulfoxide and the like. It is done. The reaction temperature is preferably between room temperature and 250 ° C. In addition, the pH can be adjusted to promote the reaction. For pH adjustment, a buffer solution prepared by mixing a basic aqueous solution such as lithium hydroxide, potassium hydroxide, or sodium hydroxide with an acid such as phosphoric acid is used.

Specifically, for example, in the first step; a naphthalene-1,4,5,8-tetracarboxylic dianhydride derivative and a 1,1-disubstituted hydrazine derivative are reacted to produce a monoimide body; In two steps; by reacting the monoimide body with the first hydrazine derivative having a different substituent, R ¹ and R ² in the naphthalenetetracarboxylic acid diimide derivative represented by the general formula (1) Derivatives having different R ³ and R ⁴ can be produced.

Alternatively, 1 mole equivalent of naphthalenetetracarboxylic dianhydride and 2 mole equivalent or more of hydrazine derivative are reacted to form R ¹ , R ² and R ³ , R ^{4 in the} naphthalene tetracarboxylic acid diimide derivative represented by the general formula (1). Can produce the same derivatives.

Specific examples of the alkyl group in the description of the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an undecanyl group. In addition, aromatic hydrocarbon groups include aromatic ring groups such as benzene, biphenyl, naphthalene, anthracene, fluorene, and pyrene, and aromatic heterocyclic groups such as pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole. Groups.
These substituents include those exemplified in the above specific examples of alkyl groups, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, or halogen atoms of fluorine atom, chlorine atom, bromine atom and iodine atom. Atoms, dialkylamino groups, diphenylamino groups, the aromatic hydrocarbon groups, and heterocyclic groups such as pyrrolidine, piperidine, piperazine and the like can be mentioned.
Further, when R ¹ and R ² are bonded to each other to form a heterocyclic group containing a nitrogen atom, the heterocyclic group is a condensed heterocyclic ring in which an aromatic hydrocarbon group is condensed to a pyrrolidino group, piperidino group, piperazino group or the like. The group can be mentioned.

  Preferred examples of general formula (1) are given below. However, the present invention is not limited to these compounds.

Next, the layer structure of the electrophotographic photosensitive member will be described.
FIG. 1 is a sectional view showing an electrophotographic photosensitive member of the present invention. A photosensitive layer 33 mainly composed of a charge generating material and a charge transporting material is provided on a conductive support 31.

  FIG. 2 shows a structure in which a charge generation layer 35 mainly composed of a charge generation material and a charge transport layer 37 mainly composed of a charge transport material are laminated on a conductive support 31. .

  In FIG. 3, a photosensitive layer 33 mainly composed of a charge generation material and a charge transport material is provided on a conductive support 31, and a protective layer 39 is further provided on the surface of the photosensitive layer. In this case, the protective layer 39 may contain the naphthalene tetracarboxylic acid diimide derivative of the present invention.

  FIG. 4 shows a structure in which a charge generation layer 35 mainly composed of a charge generation material and a charge transport layer 37 mainly composed of a charge transport material are laminated on a conductive support 31. A protective layer 39 is provided on the charge transport layer. In this case, the protective layer 39 may contain the naphthalene tetracarboxylic acid diimide derivative of the present invention.

  FIG. 5 shows a structure in which a charge transport layer 37 mainly composed of a charge transport material and a charge generation layer 35 mainly composed of a charge generation material are laminated on a conductive support 31.

  FIG. 6 shows a structure in which a charge transport layer 37 mainly composed of a charge transport material and a charge generation layer 35 mainly composed of a charge generation material are laminated on a conductive support 31. Further, a protective layer 39 is provided on the charge generation layer. In this case, the protective layer 39 may contain the naphthalene tetracarboxylic acid diimide derivative of the present invention.

Examples of the conductive support 31 include those having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, indium oxide, etc. The metal oxide of the above is coated with film or cylindrical plastic or paper by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel or the like and extruded by drawing or drawing. After pipe formation, surface treatment pipes such as cutting, superfinishing, and polishing can be used. Further, an endless nickel belt or an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can also be used as the conductive support 31.

  In addition, a material obtained by dispersing conductive powder in an appropriate binder resin and coating it on the support can also be used as the conductive support 31 of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support 31 of the present invention.

  Next, the photosensitive layer will be described. The photosensitive layer may be a single layer or a laminate, but for convenience of explanation, the case where it is composed of the charge generation layer 35 and the charge transport layer 37 will be described first.

  The charge generation layer 35 is a layer mainly composed of a charge generation material. A known charge generation material can be used for the charge generation layer 35, and representative examples thereof include C-I Pigment Blue 25 (Color Index CI 21180), C-I Pigment Red 41 (CI 21200), and C-I Acid Red 52 (CI). 45100), CI Basic Red 3 (CI 45210), azo pigments having a carbazole skeleton (described in JP-A-53-95033), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), An azo pigment having a triphenylamine skeleton (described in JP-A No. 53-132347), an azo pigment having a dibenzothiophene skeleton (described in JP-A No. 54-21728), an azo pigment having an oxadiazole skeleton ( Described in Japanese Patent Laid-Open No. 54-12742 ), An azo pigment having a fluorenone skeleton (described in JP-A-54-22834), an azo pigment having a bis-stilbene skeleton (described in JP-A-54-17733), an azo having a distyryloxadiazole skeleton Azo pigments such as pigments (described in JP-A No. 54-2129), azo pigments having a distyrylcarbazole skeleton (described in JP-A No. 54-14967), and azo pigments having a benzanthrone skeleton. For example, CI Pigment Blue 16 (CI 74100), Y-type oxotitanium phthalocyanine (Japanese Patent Laid-Open No. 64-17066), A (β) -type oxotitanium phthalocyanine, B (α) -type oxotitanium phthalocyanine, I-type oxotitanium phthalocyanine (Described in JP-A-11-21466), type II chlorogallium phthalocyanine (Iijima et al., The 67th Annual Meeting of the Chemical Society of Japan, 1B4, 04 (1994)), type V hydroxygallium phthalocyanine (Damon et al., The Chemical Society of Japan) 67th Spring Annual Meeting, 1B4, 05 (1994)), phthalocyanine pigments such as X-type metal-free phthalocyanine (U.S. Pat. No. 3,816,118), C-Ibat Brown 5 (CI 73410), C-Ibat Dye (CI) 7330) and other indigo pigments, Lugo (manufactured by Bayer Co., Ltd.) Scarlet B, such as perylene pigment, such as in-closet Ren Scarlet R (manufactured by Bayer Co., Ltd.) and the like. These materials may be used alone or in combination of two or more.

  In the charge generation layer 35, a charge generation material is dispersed in a suitable solvent together with a binder resin as necessary using a ball mill, an attritor, a sand mill, an ultrasonic wave, etc., and this is applied onto a conductive support. It is formed by drying.

  As the binder resin used for the charge generation layer 35 as necessary, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N -Vinylcarbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Can be mentioned. The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material. The binder resin may be added before or after dispersion.

  Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, and ligroin. In particular, ketone solvents, ester solvents, and ether solvents are preferably used. These may be used alone or in combination of two or more.

  The charge generation layer 35 includes a charge generation material, a solvent, and a binder resin as main components, and includes any additive such as a sensitizer, a dispersant, a surfactant, and silicone oil. Also good.

As a coating method for the coating solution, a dip coating method, spray coating, beat coating, nozzle coating, spinner coating, ring coating, or the like can be used.
The thickness of the charge generation layer 35 is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.

  The charge transport layer 37 is a layer mainly composed of a charge transport material. The charge transport material is divided into a hole transport material, an electron transport material, and a polymer charge transport material, which will be described below.

  Examples of the hole transport material include poly-N-carbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, imidazole There are derivatives, triphenylamine derivatives, and compounds represented by the following general formulas (11) to (34).

（式中、Ｒ１はメチル基、エチル基、２−ヒドロキシエチル基または２−クロルエチル基を表し、Ｒ２はメチル基、エチル基、ベンジル基またはフェニル基を表し、Ｒ３は水素原子、塩素原子、臭素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ジアルキルアミノ基またはニトロ基を表す。）
一般式（１１）で表される化合物には、例えば、９−エチルカルバゾール−３−カルボアルデヒド１−メチル−１−フェニルヒドラゾン、９−エチルカルバゾール−３−カルボアルデヒド １−ベンジル−１−フェニルヒドラゾン、９−エチルカルバゾール−３−カルボアルデヒド １、１−ジフェニルヒドラゾンなどがある

(Wherein R1 represents a methyl group, an ethyl group, a 2-hydroxyethyl group or a 2-chloroethyl group, R2 represents a methyl group, an ethyl group, a benzyl group or a phenyl group, and R3 represents a hydrogen atom, a chlorine atom, a bromine group) Represents an atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group, or a nitro group.)
Examples of the compound represented by the general formula (11) include 9-ethylcarbazole-3-carbaldehyde 1-methyl-1-phenylhydrazone, 9-ethylcarbazole-3-carbaldehyde 1-benzyl-1-phenylhydrazone. , 9-ethylcarbazole-3-carbaldehyde 1,1-diphenylhydrazone, etc.

（式中、Ａｒはナフタレン環、アントラセン環、ピレン環及びそれらの置換体あるいはピリジン環、フラン環、チオフェン環を表し、Ｒはアルキル基、フェニル基またはベンジル基を表す。）
一般式（１２）で表される化合物には、例えば、４−ジエチルアミノスチリル−β−カルボアルデヒド １−メチル−１−フェニルヒドラゾン、４−メトキシナフタレン−１−カルボアルデヒド １−ベンジル−１−フェニルヒドラゾンなどがある。

(In the formula, Ar represents a naphthalene ring, anthracene ring, pyrene ring and a substituted product thereof, or a pyridine ring, a furan ring, and a thiophene ring, and R represents an alkyl group, a phenyl group, or a benzyl group.)
Examples of the compound represented by the general formula (12) include 4-diethylaminostyryl-β-carbaldehyde 1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-carbaldehyde 1-benzyl-1-phenylhydrazone. and so on.

（式中、Ｒ１はアルキル基、ベンジル基、フェニル基またはナフチル基を表し、 Ｒ２は水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、ジアルキルアミノ基、ジアラルキルアミノ基またはジアリールアミノ基を表し、ｎは１〜４の整数を表し、ｎが２以上のときはＲ２は同じでも異なっていても良い。 Ｒ３は水素原子またはメトキシ基を表す。）
一般式（１３）で表される化合物には、例えば、４−メトキシベンズアルデヒド １−メチル−１−フェニルヒドラゾン、２、４−ジメトキシベンズアルデヒド １−ベンジル−１−フェニルヒドラゾン、４−ジエチルアミノベンズアルデヒド １、１−ジフェニルヒドラゾン、４−メトキシベンズアルデヒド １−（４−メトキシ）フェニルヒドラゾン、４−ジフェニルアミノベンズアルデヒド １−ベンジル−１−フェニルヒドラゾン、４−ジベンジルアミノベンズアルデヒド １、１−ジフェニルヒドラゾンなどがある。

(Wherein R1 represents an alkyl group, a benzyl group, a phenyl group or a naphthyl group, R2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, a diaralkylamino group) Represents a group or a diarylamino group, n represents an integer of 1 to 4, and when n is 2 or more, R2 may be the same or different, and R3 represents a hydrogen atom or a methoxy group.
Examples of the compound represented by the general formula (13) include 4-methoxybenzaldehyde 1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldehyde 1-benzyl-1-phenylhydrazone, 4-diethylaminobenzaldehyde 1,1. -Diphenylhydrazone, 4-methoxybenzaldehyde 1- (4-methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde 1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde 1,1-diphenylhydrazone and the like.

（式中、 Ｒ１は炭素数１〜１１のアルキル基、置換もしくは無置換のフェニル基または複素環基を表し、 Ｒ２、Ｒ３はそれぞれ同一でも異なっていてもよく、水素原子、炭素数１〜４のアルキル基、ヒドロキシアルキル基、クロルアルキル基または置換もしくは無置換のアラルキル基を表し、また、Ｒ２とＲ３は互いに結合し窒素を含む複素環を形成していても良い。 Ｒ４は同一でも異なっていてもよく、水素原子、炭素数１〜４のアルキル基、アルコキシ基またはハロゲン原子を表す。）
一般式（１４）で表される化合物には、例えば、１、１−ビス（４−ジベンジルアミノフェニル）プロパン、トリス（４−ジエチルアミノフェニル）メタン、１、１−ビス（４−ジベンジルアミノフェニル）プロパン、２，２’−ジメチル−４，４’−ビス（ジエチルアミノ）−トリフェニルメタンなどがある。

(In the formula, R1 represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group or a heterocyclic group, and R2 and R3 may be the same as or different from each other; And an alkyl group, a hydroxyalkyl group, a chloroalkyl group, or a substituted or unsubstituted aralkyl group, and R2 and R3 may be bonded to each other to form a nitrogen-containing heterocyclic ring. And represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom.)
Examples of the compound represented by the general formula (14) include 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4-dibenzylamino). Phenyl) propane, 2,2′-dimethyl-4,4′-bis (diethylamino) -triphenylmethane, and the like.

（式中、Ｒは水素原子またはハロゲン原子を表し、Ａｒは置換もしくは無置換のフェニル基、ナフチル基、アントリル基またはカルバゾリル基を表す。）
一般式（１５）で表される化合物には、例えば、９−（４−ジエチルアミノスチリル）アントラセン、９−ブロム−１０−（４−ジエチルアミノスチリル）アントラセンなどがある。

(In the formula, R represents a hydrogen atom or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or carbazolyl group.)
Examples of the compound represented by the general formula (15) include 9- (4-diethylaminostyryl) anthracene and 9-bromo-10- (4-diethylaminostyryl) anthracene.

（式中、 Ｒ１は水素原子、ハロゲン原子、シアノ基、炭素数１〜４のアルコキシ基または炭素数１〜４のアルキル基を表し、Ａｒは下記一般式（１７）、一般式（１８）を表す。

(In the formula, R1 represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and Ar represents the following general formula (17) and general formula (18). Represent.

Ｒ２は炭素数１〜４のアルキル基を表し、Ｒ３は水素原子、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはジアルキルアミノ基を表し、ｎは１または２であって、ｎが２のときはＲ３は同一でも異なっていてもよく、Ｒ４、Ｒ５は水素原子、炭素数１〜４の置換もしくは無置換のアルキル基または置換もしくは無置換のベンジル基を表す。）
一般式（１６）で表される化合物には、例えば、９−（４−ジメチルアミノベンジリデン）フルオレン、３−（９−フルオレニリデン）−９−エチルカルバゾールなどがある。

R2 represents an alkyl group having 1 to 4 carbon atoms, R3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a dialkylamino group, and n is 1 or 2 And when n is 2, R3 may be the same or different, and R4 and R5 each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted benzyl group. . )
Examples of the compound represented by the general formula (16) include 9- (4-dimethylaminobenzylidene) fluorene and 3- (9-fluorenylidene) -9-ethylcarbazole.

（式中、Ｒはカルバゾリル基、ピリジル基、チエニル基、インドリル基、フリル基あるいはそれぞれ置換もしくは非置換のフェニル基、スチリル基、ナフチル基、またはアントリル基であって、これらの置換基がジアルキルアミノ基、アルキル基、アルコキシ基、カルボキシ基またはそのエステル、ハロゲン原子、シアノ基、アラルキルアミノ基、N-アルキル-N-アラルキルアミノ基、アミノ基、ニトロ基及びアセチルアミノ基からなる群から選ばれた基を表す。）
一般式（１９）で表される化合物には、例えば、１、２−ビス（４−ジエチルアミノスチリル）ベンゼン、１、２−ビス（２、４−ジメトキシスチリル）ベンゼンなどがある。

Wherein R is a carbazolyl group, pyridyl group, thienyl group, indolyl group, furyl group or a substituted or unsubstituted phenyl group, styryl group, naphthyl group, or anthryl group, and these substituents are dialkylamino Selected from the group consisting of a group, an alkyl group, an alkoxy group, a carboxy group or an ester thereof, a halogen atom, a cyano group, an aralkylamino group, an N-alkyl-N-aralkylamino group, an amino group, a nitro group, and an acetylamino group Represents a group.)
Examples of the compound represented by the general formula (19) include 1,2-bis (4-diethylaminostyryl) benzene and 1,2-bis (2,4-dimethoxystyryl) benzene.

（式中、 Ｒ１は低級アルキル基、置換もしくは無置換のフェニル基、またはベンジル基を表し、 Ｒ２、Ｒ３は水素原子、低級アルキル基、低級アルコキシ基、ハロゲン原子、ニトロ基、アミノ基あるいは低級アルキル基またはベンジル基で置換されたアミノ基を表し、ｎは１または２の整数を表す。）
一般式（２０）で表される化合物には、例えば、３−スチリル−９−エチルカルバゾール、３−（４−メトキシスチリル）−９−エチルカルバゾールなどがある。

(Wherein R1 represents a lower alkyl group, a substituted or unsubstituted phenyl group, or a benzyl group, and R2 and R3 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group, or a lower alkyl group. Represents an amino group substituted with a group or a benzyl group, and n represents an integer of 1 or 2.)
Examples of the compound represented by the general formula (20) include 3-styryl-9-ethylcarbazole and 3- (4-methoxystyryl) -9-ethylcarbazole.

（式中、 Ｒ１は水素原子、アルキル基、アルコキシ基またはハロゲン原子を表し、 Ｒ２およびＲ３は置換もしくは無置換のアリール基を表し、 Ｒ４は水素原子、低級アルキル基または置換もしくは無置換のフェニル基を表し、また、Ａｒは置換もしくは無置換のフェニル基またはナフチル基を表す。）
一般式（２１）で表される化合物には、例えば、４−ジフェニルアミノスチルベン、４−ジベンジルアミノスチルベン、４−ジトリルアミノスチルベン、１−（４−ジフェニルアミノスチリル）ナフタレン、１−（４−ジフェニルアミノスチリル）ナフタレンなどがある。

(Wherein R1 represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R2 and R3 represent a substituted or unsubstituted aryl group, and R4 represents a hydrogen atom, a lower alkyl group or a substituted or unsubstituted phenyl group. Ar represents a substituted or unsubstituted phenyl group or naphthyl group.)
Examples of the compound represented by the general formula (21) include 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- (4 -Diphenylaminostyryl) naphthalene.

（式中、ｎは０または１の整数、 Ｒ１は水素原子、アルキル基または置換もしくは無置換のフェニル基を表し、Ａｒ１は置換もしくは未置換のアリール基を表し、Ｒ５は置換アルキル基を含むアルキル基、あるいは置換もしくは無置換のアリール基を表し、Ａは下記一般式（２３）、一般式（２４）、９−アントリル基または置換もしくは無置換のカルバゾリル基を表す。また、ｎが０の時、ＡとＲ１は共同で環を形成しても良い。

(In the formula, n represents an integer of 0 or 1, R1 represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted phenyl group, Ar1 represents a substituted or unsubstituted aryl group, and R5 represents an alkyl containing a substituted alkyl group. Represents a group, or a substituted or unsubstituted aryl group, and A represents the following general formula (23), general formula (24), 9-anthryl group or a substituted or unsubstituted carbazolyl group, and when n is 0. , A and R1 may form a ring together.

ここでＲ２は水素原子、アルキル基、アルコキシ基、ハロゲン原子または一般式（２５）を表し、一般式（２３）では、ｍは１〜５の整数を表し、一般式（２４）では、ｍは１〜７の整数を表し、ｍが２以上の時Ｒ２は同一でも異なっても良い

Here, R2 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or general formula (25). In general formula (23), m represents an integer of 1 to 5, and in general formula (24), m is Represents an integer of 1 to 7, and when m is 2 or more, R2 may be the same or different.

（ただし、Ｒ３およびＲ４は置換もしくは無置換のアリール基を示し、 Ｒ３およびＲ４は同じでも異なっていてもよく、 Ｒ４は環を形成しても良い）。）
一般式（２２）で表される化合物には、例えば、４‘−ジフェニルアミノ−α−フェニルスチルベン、４‘−ビス（４−メチルフェニル）アミノ−α−フェニルスチルベンなどがある。

(However, R3 and R4 represent a substituted or unsubstituted aryl group, R3 and R4 may be the same or different, and R4 may form a ring). )
Examples of the compound represented by the general formula (22) include 4′-diphenylamino-α-phenylstilbene and 4′-bis (4-methylphenyl) amino-α-phenylstilbene.

（式中、Ｒ１、Ｒ２およびＲ３は水素原子、低級アルキル基、低級アルコキシ基、ハロゲン原子またはジアルキルアミノ基を表し、ｎは０または１を表す。）
一般式（２６）で表される化合物には、例えば、１−フェニル−３−（４−ジエチルアミノスチリル）−５−（４−ジエチルアミノフェニル）ピラゾリンなどがある。

(Wherein R1, R2 and R3 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a dialkylamino group, and n represents 0 or 1)
Examples of the compound represented by the general formula (26) include 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline.

（式中、 Ｒ１およびＲ２は置換アルキル基を含むアルキル基、または置換もしくは未置換のアリール基を表し、 Ａは置換アミノ基、置換もしくは未置換のアリール基またはアリル基を表す。）
一般式（２７）で表される化合物には、例えば、２、５−ビス（４−ジエチルアミノフェニル）−１，３，４−オキサジアゾール、２−Ｎ、Ｎ−ジフェニルアミノ−５−（４−ジエチルアミノフェニル）−１，３，４−オキサジアゾール、２−（４−ジメチルアミノフェニル）−５−（４−ジエチルアミノフェニル）−１，３，４−オキサジアゾールなどがある。

(Wherein R1 and R2 represent an alkyl group containing a substituted alkyl group or a substituted or unsubstituted aryl group, and A represents a substituted amino group, a substituted or unsubstituted aryl group or an allyl group.)
Examples of the compound represented by the general formula (27) include 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 2-N, N-diphenylamino-5- (4 -Diethylaminophenyl) -1,3,4-oxadiazole, 2- (4-dimethylaminophenyl) -5- (4-diethylaminophenyl) -1,3,4-oxadiazole and the like.

（式中、Ｘは水素原子、低級アルキル基またはハロゲン原子を表し、Ｒは置換アルキル基を含むアルキル基、または置換もしくは無置換のアリール基を表し、 Ａは置換アミノ基または置換もしくは無置換のアリール基を表す。）
一般式（２８）で表される化合物には、例えば、２−Ｎ、Ｎ−ジフェニルアミノ−５−（Ｎ−エチルカルバゾール−３−イル）−１，３，４−オキサジアゾール、２−（４−ジエチルアミノフェニル）−５−（Ｎ−エチルカルバゾール−３−イル）−１，３，４−オキサジアゾールなどがある。

(In the formula, X represents a hydrogen atom, a lower alkyl group or a halogen atom, R represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group or a substituted or unsubstituted group. Represents an aryl group.)
Examples of the compound represented by the general formula (28) include 2-N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2- ( 4-diethylaminophenyl) -5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole.

（式中、 Ｒ１は低級アルキル基、低級アルコキシ基またはハロゲン原子を表し、Ｒ２、Ｒ３は同じでも異なっていてもよく、水素原子、低級アルキル基、低級アルコキシ基またはハロゲン原子を表し、ｌ、ｍ、ｎは０〜４の整数を表す。）
一般式（２９）で表されるベンジジン化合物には、例えば、Ｎ，Ｎ’−ジフェニル− Ｎ，Ｎ’−ビス（３−メチルフェニル）−[１，１’−ビフェニル]−４，４’−ジアミン、３，３’−ジメチル−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（４−メチルフェニル）−[１，１’−ビフェニル]−４，４’−ジアミンなどがある。

(Wherein R1 represents a lower alkyl group, a lower alkoxy group or a halogen atom, R2 and R3 may be the same or different, and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom; , N represents an integer of 0-4.)
Examples of the benzidine compound represented by the general formula (29) include N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-. Examples include diamine, 3,3′-dimethyl-N, N, N ′, N′-tetrakis (4-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine.

（式中、 Ｒ１、Ｒ３およびＲ４は水素原子、アミノ基、アルコキシ基、チオアルコキシ基、アリールオキシ基、メチレンジオキシ基、置換もしくは無置換のアルキル基、ハロゲン原子または置換もしくは無置換のアリール基を、Ｒ２は水素原子、アルコキシ基、置換もしくは無置換のアルキル基またはハロゲン原子を表す。ただし、 Ｒ１、Ｒ２、Ｒ３およびＲ４はすべて水素原子である場合は除く。また、ｋ，ｌ，ｍおよびｎは１、２、３または４の整数であり、それぞれが２、３または４の整数の時は、前記Ｒ１、Ｒ２、Ｒ３およびＲ４は同じでも異なっていても良い。）
一般式（３０）で表されるビフェニリルアミン化合物には、例えば、４’−メトキシ− Ｎ，Ｎ−ジフェニル−[１，１’−ビフェニル]−４−アミン、４’−メチル− Ｎ，Ｎ−ビス（４−メチルフェニル）−[１，１’−ビフェニル]−４−アミン、４’−メトキシ− Ｎ，Ｎ−ビス（４−メチルフェニル）−［１，１’−ビフェニル］−４−アミン、Ｎ，Ｎ−ビス（３，４−ジメチルフェニル）−［１，１‘−ビフェニル］−4−アミンなどがある。

Wherein R1, R3 and R4 are a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom or a substituted or unsubstituted aryl group. R2 represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group or a halogen atom, except that R1, R2, R3 and R4 are all hydrogen atoms, and k, l, m and n is an integer of 1, 2, 3 or 4, and when each is an integer of 2, 3 or 4, the R1, R2, R3 and R4 may be the same or different.
Examples of the biphenylylamine compound represented by the general formula (30) include 4′-methoxy-N, N-diphenyl- [1,1′-biphenyl] -4-amine, 4′-methyl-N, N. -Bis (4-methylphenyl)-[1,1'-biphenyl] -4-amine, 4'-methoxy-N, N-bis (4-methylphenyl)-[1,1'-biphenyl] -4- Amines, N, N-bis (3,4-dimethylphenyl)-[1,1′-biphenyl] -4-amine, and the like.

（式中、Ａｒは置換基を有してもよい炭素数１８個以下の縮合多環式炭化水素基を表し、また、 Ｒ１およびＲ２は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。ｎは１もしくは２の整数を表す。）
一般式（３１）で表されるトリアリールアミン化合物には、例えば、Ｎ，Ｎ−ジフェニル−ピレン−１−アミン、Ｎ，Ｎ−ジ−ｐ−トリル−ピレン−１−アミン、Ｎ，Ｎ−ジ−ｐ−トリル−１−ナフチルアミン、Ｎ，Ｎ−ジ（ｐ−トリル）−１−フェナントリルアミン、９，９−ジメチル−２−（ジ−ｐ−トリルアミノ）フルオレン、Ｎ，Ｎ，Ｎ‘，Ｎ’−テトラキス（４−メチルフェニル）−フェナントレン−９，１０−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（３−メチルフェニル）−ｍ−フェニレンジアミンなどがある。

(In the formula, Ar represents an optionally substituted condensed polycyclic hydrocarbon group having 18 or less carbon atoms, and R1 and R2 are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, And represents an alkoxy group or a substituted or unsubstituted phenyl group, which may be the same or different, and n represents an integer of 1 or 2.)
Examples of the triarylamine compound represented by the general formula (31) include N, N-diphenyl-pyrene-1-amine, N, N-di-p-tolyl-pyren-1-amine, and N, N- Di-p-tolyl-1-naphthylamine, N, N-di (p-tolyl) -1-phenanthrylamine, 9,9-dimethyl-2- (di-p-tolylamino) fluorene, N, N, N Examples include ', N'-tetrakis (4-methylphenyl) -phenanthrene-9,10-diamine and N, N, N', N'-tetrakis (3-methylphenyl) -m-phenylenediamine.

（式中、Ａｒは置換もしくは無置換の芳香族炭化水素基を表し、Ａは一般式（３３）を表す。

(In the formula, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and A represents the general formula (33).

（ただし、Ａｒ’は置換もしくは無置換の芳香族炭化水素基を表し、 Ｒ１および
Ｒ２は置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基である。）
を表す。）
一般式（３２）で表されるジオレフィン芳香族化合物には、例えば、１、４−ビス（４−ジフェニルアミノスチリル）ベンゼン、１、４−ビス[４−ジ（ｐ−トリル）アミノスチリル]ベンゼンなどがある。

(However, Ar ′ represents a substituted or unsubstituted aromatic hydrocarbon group, and R1 and R2 are a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
Represents. )
Examples of the diolefin aromatic compound represented by the general formula (32) include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) aminostyryl]. There is benzene.

（式中、 Ａｒは置換もしくは無置換の芳香族炭化水素基を、 Ｒは水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表す。ｎは０または１、ｍは１または２であって、ｎ＝０、ｍ＝１の場合、 ＡｒとＲは共同で環を形成しても良い。）
一般式（３４）で表されるスチリルピレン化合物には、例えば、１−（４−ジフェニルアミノスチリル）ピレン、１−（Ｎ，Ｎ−ジ−p−トリル−４−アミノスチリル）ピレンなどがある。

(In the formula, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. N represents 0 or 1, and m represents When 1 or 2 and n = 0 and m = 1, Ar and R may form a ring together.)
Examples of the styrylpyrene compound represented by the general formula (34) include 1- (4-diphenylaminostyryl) pyrene and 1- (N, N-di-p-tolyl-4-aminostyryl) pyrene.

Examples of the electron transport material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-indeno4H-indeno [1,2-b] thiophen-4-one, 1,3 , 7-trinitrodibenzothiophene-5,5-dioxide and the like, and the electron transport materials listed in the following general formulas (35), (36), (37) and (38) are preferably used. be able to.
These charge transport materials may be used alone or in combination of two or more.

（式中Ｒ１、Ｒ２およびＲ３は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。）

(Wherein R1, R2 and R3 represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a substituted or unsubstituted phenyl group, which may be the same or different.)

（式中Ｒ１、Ｒ２は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。）

(Wherein R1 and R2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and may be the same or different.)

（式中Ｒ１、Ｒ２およびＲ３は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。）

(Wherein R1, R2 and R3 represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a substituted or unsubstituted phenyl group, which may be the same or different.)

〔式中、Ｒ１ は置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を示し、Ｒ２ は置換基を有してもよいアルキル基、置換基を有してもよいアリール基、または下記式一般式（３９）で表される基を示す。

[Wherein R1 represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R2 has an alkyl group which may have a substituent or a substituent. Or a group represented by the following formula (39).

Ｒ３ は、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を示す。〕

R3 represents an alkyl group which may have a substituent, or an aryl group which may have a substituent. ]

  As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins.

  When the charge transport material and the naphthalene tetracarboxylic acid diimide derivative of the present invention are mixed and contained in the charge transport layer, the total amount is 20 to 300 parts by weight, preferably 40 to 150 parts by weight based on 100 parts by weight of the binder resin. Part by weight is appropriate. The thickness of the charge transport layer is preferably 25 μm or less from the viewpoint of resolution and responsiveness. Regarding the lower limit, although it differs depending on the system to be used (particularly the charging potential), it is preferably 5 μm or more.

The amount of the naphthalene tetracarboxylic acid diimide derivative of the present invention is preferably 0.01 wt% to 150 wt% with respect to the charge transport material. If the amount is too small, the resistance to the oxidizing gas is insufficient.
As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used. The charge transport materials may be used alone or in combination of two or more.

  As the antioxidant that can be used in the present invention, a general antioxidant described later can be used, and (c) hydroquinone-based compounds and (f) hindered amine-based compounds are particularly effective. However, the antioxidant used here is used for alteration protection of the naphthalenetetracarboxylic acid diimide derivative used in the present invention, unlike the purpose described later. For this reason, these antioxidants are preferably contained in the coating liquid in the step before containing the naphthalene tetracarboxylic acid diimide derivative of the present invention. On the other hand, a sufficient effect can be exhibited at 0.1 to 200 wt%.

  For the charge transport layer, a polymer charge transport material having a function as a charge transport material and a function as a binder resin is also preferably used. The charge transport layer composed of these polymer charge transport materials is excellent in wear resistance. As the polymer charge transport material, known materials can be used, and in particular, a polycarbonate containing a triarylamine structure in the main chain and / or side chain is preferably used. Among these, polymer charge transport materials represented by the structural formulas (I) to (XIII) are preferably used. These are illustrated below and specific examples are shown.

式中、Ｒ１，Ｒ２，Ｒ３ はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子、Ｒ４は水素原子又は置換もしくは無置換のアルキル基、Ｒ５ ，Ｒ６ は置換もしくは無置換のアリール基、ｏ，ｐ，ｑはそれぞれ独立して０〜４の整数、ｋ，ｊは組成を表し、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表し５〜５０００の整数である。Ｘは脂肪族の２価基、環状脂肪族の２価基、または下記構造式（II）で表される２価基を表す。

In the formula, R1, R2 and R3 are each independently a substituted or unsubstituted alkyl group or a halogen atom, R4 is a hydrogen atom or a substituted or unsubstituted alkyl group, R5 and R6 are substituted or unsubstituted aryl groups, o , P, q are each independently an integer of 0-4, k, j represents a composition, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, and n represents the number of repeating units of 5-5000. It is an integer. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following structural formula (II).

式中、Ｒ１０１，Ｒ１０２ は各々独立して置換もしくは無置換のアルキル基、アリール基またはハロゲン原子を表す。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ２−，−ＣＯ−，−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表す。）または、下記構造式（III）を表す。

In the formula, R101 and R102 each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO2-, —CO—, —CO—O—Z—O—CO— (wherein Z represents an aliphatic divalent group) or the following structural formula (III).

（式中、ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ１０３、Ｒ１０４は置換または無置換のアルキル基又はアリール基を表す。）を表す。ここで、 Ｒ１０１ とＲ１０２，Ｒ１０３とＲ１０４は、それぞれ同一でも異なってもよい。

(Wherein, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R103 and R104 represent a substituted or unsubstituted alkyl group or aryl group). Here, R101 and R102, and R103 and R104 may be the same or different.

式中、Ｒ７, Ｒ８は置換もしくは無置換のアリール基、Ａｒ１, Ａｒ２, Ａｒ３は同一あるいは異なるアリレン基を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R7 and R8 represent substituted or unsubstituted aryl groups, and Ar1, Ar2, and Ar3 represent the same or different arylene groups. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ９, Ｒ１０は置換もしくは無置換のアリール基、Ａｒ４ ，Ａｒ５，Ａｒ６ は同一あるいは異なるアリレン基を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R9 and R10 represent substituted or unsubstituted aryl groups, and Ar4, Ar5 and Ar6 represent the same or different arylene groups. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ１１, Ｒ１２ は置換もしくは無置換のアリール基、Ａｒ７, Ａｒ８, Ａｒ９は同一あるいは異なるアリレン基、ｐは１〜５の整数を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R11 and R12 are substituted or unsubstituted aryl groups, Ar7, Ar8 and Ar9 are the same or different arylene groups, and p represents an integer of 1 to 5. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ１３， Ｒ１４は置換もしくは無置換のアリール基、Ａｒ１０， Ａｒ１１， Ａｒ１２は同一あるいは異なるアリレン基、 Ｘ１， Ｘ２ は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R13 and R14 are substituted or unsubstituted aryl groups, Ar10, Ar11 and Ar12 are the same or different arylene groups, X1 and X2 are substituted or unsubstituted ethylene groups, or substituted or unsubstituted vinylene groups. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ１５，Ｒ１６，Ｒ１７，Ｒ１８は置換もしくは無置換のアリール基、Ａｒ１３， Ａｒ１４，Ａｒ１５，Ａｒ１６は同一あるいは異なるアリレン基、 Ｙ１，Ｙ２，Ｙ３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表し同一であっても異なってもよい。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R15, R16, R17 and R18 are substituted or unsubstituted aryl groups, Ar13, Ar14, Ar15 and Ar16 are the same or different arylene groups, Y1, Y2 and Y3 are single bonds, substituted or unsubstituted alkylene groups, It represents a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, which may be the same or different. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ１９，Ｒ２０ は水素原子、置換もしくは無置換のアリール基を表し，Ｒ１９とＲ２０は環を形成していてもよい。Ａｒ１７，Ａｒ１８，Ａｒ１９ は同一あるいは異なるアリレン基を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R19 and R20 each represent a hydrogen atom or a substituted or unsubstituted aryl group, and R19 and R20 may form a ring. Ar17, Ar18 and Ar19 represent the same or different arylene groups. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ２１は置換もしくは無置換のアリール基、Ａｒ２０，Ａｒ２１，Ａｒ２２，Ａｒ２３ は同一あるいは異なるアリレン基を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R21 represents a substituted or unsubstituted aryl group, and Ar20, Ar21, Ar22, Ar23 represent the same or different arylene groups. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ２２，Ｒ２３，Ｒ２４，Ｒ２５は置換もしくは無置換のアリール基、Ａｒ２４，Ａｒ２５，Ａｒ２６，Ａｒ２７，Ａｒ２８は同一あるいは又は異なるアリレン基を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R22, R23, R24 and R25 represent substituted or unsubstituted aryl groups, and Ar24, Ar25, Ar26, Ar27 and Ar28 represent the same or different arylene groups. X, k, j and n are the same as in the case of the above structural formula (I).

式中、Ｒ２６，Ｒ２７ は置換もしくは無置換のアリール基、 Ａｒ２９，Ａｒ３０，Ａｒ３１は同一あるいは異なるアリレン基を表す。 Ｘ，ｋ，ｊおよびｎは、上記構造式（I）式の場合と同じである。

In the formula, R26 and R27 represent a substituted or unsubstituted aryl group, and Ar29, Ar30, and Ar31 represent the same or different arylene groups. X, k, j and n are the same as those in the above formula (I).

（式中、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４およびＡｒ５は置換もしくは無置換の芳香環基、Ｚは芳香環基または―Ａｒ６―Ｚａ―Ａｒ６―を表し、 Ａｒ６は置換もしくは無置換の芳香環基、ＺａはＯ、Ｓまたはアルキレン基、ＲおよびＲ’は直鎖又は分岐鎖のアルキレン基を表す。 ｍは０または１を表す。ｋ、ｊ、ｎ及びＸは前式と同じ。）

(In the formula, Ar1, Ar2, Ar3, Ar4 and Ar5 represent a substituted or unsubstituted aromatic ring group, Z represents an aromatic ring group or -Ar6-Za-Ar6-, Ar6 represents a substituted or unsubstituted aromatic ring group, Za represents O, S or an alkylene group, R and R ′ each represents a linear or branched alkylene group, m represents 0 or 1, and k, j, n and X are the same as in the previous formula.)

The charge transport layer 37 can be formed by dissolving or dispersing a charge transport material alone or in a binder resin and an appropriate solvent, and applying and drying this on the charge generation layer. Further, if necessary, two or more kinds of plasticizers, leveling agents, antioxidants and the like can be added.
As a coating method of the coating liquid obtained as described above, conventional coating methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.

  Next, the case where the photosensitive layer has a single layer structure 33 will be described. A photoreceptor in which the above-described charge generating material is dispersed in a binder resin can be used. The photosensitive layer can be formed by dissolving or dispersing a charge generating substance, a charge transporting substance, and a binder resin in a suitable solvent, and applying and drying them. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.

  As the binder resin, in addition to the binder resin previously mentioned in the charge transport layer 37, the binder resin mentioned in the charge generation layer 35 may be mixed and used. Of course, the polymer charge transport materials mentioned above can also be used favorably. The amount of the charge generating material with respect to 100 parts by weight of the binder resin is preferably 5 to 40 parts by weight, and the amount of the charge transporting material is preferably 0 to 190 parts by weight, and more preferably 50 to 150 parts by weight. The photosensitive layer is formed by dip coating, spray coating, bead coating, a coating solution in which a charge generating material and a binder resin are dispersed together with a charge transporting material using a solvent such as tetrahydrofuran, dioxane, dichloroethane, and cyclohexane. It can be formed by coating with a ring coat or the like. The film thickness of the photosensitive layer is suitably about 5 to 25 μm.

  In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support 31 and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect 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 resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment 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 a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodization, organic substances such as polyparaxylylene (parylene), SiO ₂ , 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. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

  In the photoreceptor of the present invention, the protective layer 39 may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. Materials used for the protective layer 39 are ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, aryl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene. , Polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, polyarylate, AS resin, butadiene-styrene copolymer, polyurethane, poly Examples thereof include resins such as vinyl chloride, polyvinylidene chloride, and epoxy resin. From the viewpoint of filler dispersibility, residual potential, and coating film defects, polycarbonate or polyarylate is particularly effective and useful.

A filler material is added to the protective layer of the photoreceptor for the purpose of improving the wear resistance.
As the solvent to be used, all solvents used in the charge transport layer 37 such as tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, and acetone can be used. However, a solvent having a high viscosity is preferable at the time of dispersion, but a solvent having high volatility is preferable at the time of coating. When there is no solvent satisfying these conditions, it is possible to use a mixture of two or more solvents having respective physical properties, which may have a great effect on filler dispersibility and residual potential. .

  Moreover, the amine compound of this invention may be contained in the protective layer. Furthermore, the addition of the low molecular charge transport material or the polymer charge transport material mentioned in the charge transport layer 37 is effective and useful for reducing the residual potential and improving the image quality.

  As a method for forming the protective layer, conventional methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, etc. can be used. preferable.

  In the photoreceptor of the present invention, an 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 generally used coating method as described above is employed. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

  In the present invention, in order to improve environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, oxidation is performed on each layer such as a charge generation layer, a charge transport layer, an undercoat layer, a protective layer, and an intermediate layer. Inhibitors, plasticizers, lubricants, UV absorbers and leveling agents can be added. Representative materials of these compounds are described below.

  Examples of the antioxidant that can be added to each layer include, but are not limited to, the following.

(A) Phenolic compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl -3- (4'-hydroxy-3 ', 5'-di-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'- Methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl) -6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [meth -3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3′-t-butylphenyl) ) Butyric acid] cricol ester, tocopherols and the like.

(B) Paraphenylenediamines N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylene Diamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.

(C) Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2 -(2-octadecenyl) -5-methylhydroquinone and the like.

(D) Organic sulfur compounds Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.

(E) Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

  Examples of the plasticizer that can be added to each layer include, but are not limited to, the following.

(A) Phosphate ester plasticizer Triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, Triphenyl phosphate etc.

(B) Phthalate ester plasticizers Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, phthalate Dinonyl acid, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, octyl decyl phthalate, dibutyl fumarate, dioctyl fumarate Such.

(C) Aromatic carboxylic acid ester plasticizers Trioctyl trimellitic acid, tri-n-octyl trimellitic acid, octyl oxybenzoate, and the like.

(D) Aliphatic dibasic ester plasticizer dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, adipic acid n-octyl-n-decyl , Diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2 sebacate -Ethoxyethyl, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, di-n-octyl tetrahydrophthalate and the like.

(E) Fatty acid ester derivatives butyl oleate, glycerin monooleate, methyl acetylricinoleate, pentaerythritol ester, dipentaerythritol hexaester, triacetin, tributyrin and the like.

(F) Oxyacid ester plasticizers Methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, tributyl acetyl citrate and the like.

(G) Epoxy plasticizer Epoxidized soybean oil, epoxidized linseed oil, butyl epoxy stearate, decyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, dioctyl epoxy hexahydrophthalate, didecyl epoxy hexahydrophthalate, etc. .

(H) Dihydric alcohol ester plasticizers such as diethylene glycol dibenzoate and triethylene glycol di-2-ethylbutyrate.

(I) Chlorinated plasticizer Chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl, methoxychlorinated fatty acid methyl and the like.

(J) Polyester plasticizer Polypropylene adipate, polypropylene sebacate, polyester, acetylated polyester and the like.

(K) Sulfonic acid derivatives p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfoneethylamide, o-toluenesulfoneethylamide, toluenesulfone-N-ethylamide, p-toluenesulfone-N-cyclohexylamide and the like.

(L) Citric acid derivatives Triethyl citrate, triethyl acetylcitrate, tributyl citrate, tributyl acetylcitrate, tri-2-ethylhexyl acetylcitrate, acetylcitrate-n-octyldecyl, and the like.

(M) Others Terphenyl, partially hydrogenated terphenyl, camphor, 2-nitrodiphenyl, dinonylnaphthalene, methyl abietate and the like.

  Examples of the lubricant that can be added to each layer include, but are not limited to, the following.

(A) Hydrocarbon compounds Liquid paraffin, paraffin wax, microwax, low-polymerized polyethylene and the like.

(B) Fatty acid compounds Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like.

(C) Fatty acid amide compounds Stearylamide, palmitylamide, oleinamide, methylenebisstearamide, ethylenebisstearamide and the like.

(D) Ester compounds Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, fatty acid polyglycol esters, and the like.

(E) Alcohol compounds Cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, polyglycerol and the like.

(F) Metal soap Lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate and the like.

(G) Natural wax Carnauba wax, candelilla wax, beeswax, whale wax, ivotaro, montan wax and the like.

(H) Others Silicone compounds, fluorine compounds, etc.

  Examples of the ultraviolet absorber that can be added to each layer include, but are not limited to, the following.

(A) Benzophenone series 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ′, 4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4- Such as methoxybenzophenone.

(B) Salsylate type Phenyl salsylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.

(C) benzotriazole (2′-hydroxyphenyl) benzotriazole, (2′-hydroxy5′-methylphenyl) benzotriazole, (2′-hydroxy5′-methylphenyl) benzotriazole, (2′-hydroxy3) '-Tert-butyl-5'-methylphenyl) 5-chlorobenzotriazole

(D) Cyanoacrylate-based ethyl-2-cyano-3,3-diphenyl acrylate, methyl 2-carbomethoxy 3 (paramethoxy) acrylate, and the like.

(E) Quencher (metal complex)
Nickel (2,2′thiobis (4-t-octyl) phenolate) normal butylamine, nickel dibutyldithiocarbamate, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and the like.

(F) HALS (hindered amine)
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6 6-tetramethylpyridine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine and the like.

  Next, the electrophotographic method and the electrophotographic apparatus of the present invention will be described in detail with reference to the drawings.

FIG. 7 is a schematic view for explaining the electrophotographic process and the electrophotographic apparatus of the present invention, and the following examples also belong to the category of the present invention.
In FIG. 7, the photoreceptor 1 is provided with at least a photosensitive layer, and the outermost surface layer contains a filler. The photosensitive member 1 has a drum shape, but may be a sheet shape or an endless belt shape. As the charging charger 3, the pre-transfer charger 7, the transfer charger 10, the separation charger 11, and the pre-cleaning charger 13, a corotron, a scorotron, a solid charger (solid state charger), a charging roller, or the like is used, and known means are used. All are usable.
As the transfer means, the above charger can be generally used. However, as shown in the figure, a combination of a transfer charger and a separation charger is effective.
The light source such as the image exposure unit 5 and the charge removal lamp 2 emits light such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL). All things can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
In addition to the steps shown in FIG. 7, the light source and the like are provided with a transfer step, a static elimination step, a cleaning step, or a pre-exposure step that uses light irradiation, so that the photosensitive member is irradiated with light.
The toner developed on the photosensitive member 1 by the developing unit 6 is transferred to the transfer paper 9, but not all is transferred, and some toner remains on the photosensitive member 1. Such toner is removed from the photoreceptor by the fur brush 14 and the blade 15. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.
When a positive (negative) charge is applied to the electrophotographic photosensitive member and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. If this is developed with negative (positive) polarity toner (electrodetection fine particles), a positive image can be obtained, and if developed with positive (negative) toner, a negative image can be obtained.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.

  FIG. 8 shows another example of the electrophotographic process according to the present invention. The photoreceptor 21 has at least a photosensitive layer, and further contains a filler on the outermost surface layer. The photoreceptor 21 is driven by driving rollers 22a and 22b, and is charged by a charger 23, image exposure by a light source 24, and development (not shown). Then, transfer using the charger 25, exposure before cleaning with the light source 26, cleaning with the brush 27, and static elimination with the light source 28 are repeated. In FIG. 8, the photoconductor 21 (of course, the support is translucent in this case) is irradiated with pre-cleaning exposure light from the support side.

  The above illustrated electrophotographic process is illustrative of an embodiment of the present invention, and of course other embodiments are possible. For example, in FIG. 8, the pre-cleaning exposure is performed from the support side, but this may be performed from the photosensitive layer side, or image exposure and neutralization light irradiation may be performed from the support side.

  On the other hand, the light irradiation process is illustrated as image exposure, pre-cleaning exposure, and static elimination exposure. In addition, a pre-transfer exposure, a pre-exposure of image exposure, and other known light irradiation processes are provided to light the photosensitive member. Irradiation can also be performed.

  The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge. A process cartridge is a single device (part) that contains a photosensitive member and includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit. There are many shapes and the like of the process cartridge, but a general example is shown in FIG.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by an Example. All parts are parts by weight. Moreover, the following Example 12 and Example 27 are reference examples.

Production Example 1 (Production of Exemplified Compound No. 20)
Naphthalene-1,4,5,8-tetracarboxylic dianhydride (Tokyo Kasei Reagent) 2.68 g (10.0 mmol), N, N'-dimethylformamide 30 ml 1,1-diphenylhydrazine (Tokyo Kasei Reagent) 3.68 g (20.0 mmol) was added, and the mixture was stirred at 60 ° C. for 2 hours under an argon stream. 100 ml of water was added, and the precipitated crystals were collected by filtration and dried with a vacuum heat dryer to obtain 3.43 g (yield 57.1%) of brown crude crystals. This was subjected to silica gel column treatment [eluent: toluene / ethyl acetate (20/1) vol mixed solvent], recrystallized with toluene, dried with a vacuum heating drier, and an orange-red crystal exemplified compound No. . As a result, 7.02 g (yield 29.7%) of 20 was obtained. The elemental analysis values were as follows. DTA exothermic peak temperature with TG weight loss when the temperature is raised from room temperature at 10 ° C./min under nitrogen flow with a differential thermal calorimeter simultaneous measurement device TG / DTA6200 (manufactured by Seiko Instruments Inc.) as a decomposition point. It was 341 degreeC when measured.

Ｃ Ｈ Ｎ
実測値 ７６．０５ ４．０２ ９．２０
計算値 ７５．９９ ４．０３ ９．３３
この化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を図１０に示す。

C H N
Actual value 76.05 4.02 9.20
Calculated value 75.99 4.03 9.33
The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG.

Production Examples 2-5
Except for changing the hydrazine compound, the same procedure as in Production Example 1 was followed to obtain Exemplified Compound No. 1,10,15,37 naphthalenetetracarboxylic acid diimide derivatives were prepared. The results are shown in Table 1. Moreover, these infrared absorption spectra (KBr tablet method) are shown in FIGS.

Production Example 6 (Production of Exemplified Compound No. 38)
Under an argon stream, 2.68 g (10.0 mmol) of naphthalene-1,4,5,8-tetracarboxylic dianhydride (Tokyo Kasei Reagent) and 25 ml of N, N-dimethylformamide were heated and stirred at 80 ° C. A solution of 0.61 g (10 mmol) of 1-methyl-1-phenylhydrazine (Tokyo Kasei Reagent) and 10 ml of N, N-dimethylformamide was added dropwise thereto over 2 hours. After stirring at 80 ° C. for 30 minutes, a solution of 0.99 g (10 mmol) of 1-benzyl-1-phenylhydrazine (Tokyo Kasei Reagent) and 5 ml of N, N-dimethylformamide was added, and further stirred at 80 ° C. for 2 hours. It was. The contents were added to 100 ml of water, and the precipitated crystals were collected by filtration and dried with a vacuum heat dryer to obtain brown crude crystals. This was subjected to silica gel column treatment [eluent: toluene / ethyl acetate (10/1) vol mixed solvent], recrystallized with a toluene / ethanol mixed solvent, dried with a vacuum heating drier, and the following structural formula of maroon crystals Exemplified Compound No. 2.29 g of 38 (yield 41.4%) was obtained. The melting point was 279.5 to 280.5 ° C. The elemental analysis values were as follows.

Ｃ Ｈ Ｎ
実測値 ７３．７５ ４．１２ １０．２２
計算値 ７３．９０ ４．３８ １０．１４
この化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を図１５に示す。

C H N
Actual value 73.75 4.12 10.22
Calculated value 73.90 4.38 10.14
The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG.

Example 1
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 onto an aluminum cylinder by dip coating and dried to obtain a 3.5 μm undercoat layer, 0. A 2 μm charge generation layer and a 23 μm charge transport layer were formed (photosensitive member No. 1).
◎ Undercoat layer coating liquid Titanium dioxide powder (Ishihara Sangyo, Tybak CR-EL): 400 parts Melamine resin (Dainippon Ink, Super Becamine G821-60): 65 parts Alkyd resin (Dainippon Ink, Becko) Light M6401-50): 120 parts 2-butanone: 400 parts ◎ Charge generation layer coating solution Fluorenone bisazo pigment having the following structure: 12 parts

ポリビニルブチラール（ユニオンカーバイド製、ＸＹＨＬ）：５部
２−ブタノン：２００部
シクロヘキサノン：４００部
◎電荷輸送層塗工液
ポリカーボネート樹脂（Ｚポリカ、帝人化成製）：１０部
例示化合物Ｎｏ．４のナフタレンテトラカルボン酸ジイミド誘導体１０部
テトラヒドロフラン：１００部

Polyvinyl butyral (manufactured by Union Carbide, XYHL): 5 parts 2-butanone: 200 parts Cyclohexanone: 400 parts ◎ Charge transport layer coating solution Polycarbonate resin (Z Polyca, manufactured by Teijin Chemicals): 10 parts 4 parts of naphthalenetetracarboxylic acid diimide derivative of 4 tetrahydrofuran: 100 parts

  Remodeling imgio MF2200 manufactured by Ricoh with the electrophotographic photosensitive member manufactured as described above mounted in an electrophotographic process cartridge, the charging method being a positively charged corona charging method, and the image exposure light source being a 655 nm semiconductor laser (LD). After setting the dark part potential to 800 (V) using a machine, a repeated test corresponding to printing a total of 100,000 sheets was continuously performed. At that time, the initial image, the bright part potential after the repeated test, and the image were evaluated. In addition, for image blur (dot resolution), 10 dot images with a pixel density of 600 dpi × 600 dpi and an image density of 5% are continuously printed out, and the dot shape is observed with a stereomicroscope to increase the sharpness of the outline. The evaluation was divided into five stages (5 is excellent and 1 is inferior) according to the following criteria.

(Dot image evaluation criteria)
5: The outline is clear and good.
4: Very slight blurring of outline is observed, but good.
3: Substantially blurred outlines are observed but substantially good.
2: Blurred outlines are observed, which may be a problem depending on the type of image.
1: The dot image cannot be identified.
The results are shown in Table 2.

Examples 2-15
In Example 1, Exemplified Compound No. In the same manner as in Example 1, except that the naphthalenetetracarboxylic acid diimide derivative of No. 4 was used as shown in Table 2, the electrophotographic photoreceptor No. 2 to 15 were prepared and evaluated. The results are also shown in Table 2.

Example 16
Except that the charge transport layer coating solution in Example 1 was changed to the one having the following composition, the same procedure as in Example 1 was carried out. 16 was produced.
The evaluation was performed in the same manner as in Example 1 except that the charging method was changed to a negatively charged corona discharge (scorotron method). The results are shown in Table 3.

Charge transport layer coating solution / Polycarbonate resin (Z Polyca, manufactured by Teijin Chemicals): 10 parts 1 part of naphthalenetetracarboxylic acid diimide derivative of Exemplified Compound 4 Charge transport material No. 1 having the following structural formula 1: 9 copies

・テトラヒドロフラン：１００部

Tetrahydrofuran: 100 parts

Examples 17-30
In Example 16, Exemplified Compound No. 1 In the same manner as in Example 16, except that the naphthalene tetracarboxylic acid diimide derivative shown in Table 3 was used instead of the naphthalene tetracarboxylic acid diimide derivative of No. 4, the electrophotographic photoreceptor No. 17-30 were produced.
The results are also shown in Table 3.

Examples 31-34
Naphthalenetetracarboxylic acid diimide derivative and charge transport material No. Except that the amount of 1 was changed to the following amount, electrophotographic photoreceptors 31 to 34 were prepared and evaluated in the same manner as in Example 16. The results are also shown in Table 4.
Naphthalene tetracarboxylic acid diimide derivative: 1 part Charge transport material No. 1: 7 copies

Examples 35-38
In Examples 31-34, the charge transport material No. 1 is a charge transport material No. 1 below. Except for the change to 2, the electrophotographic photoreceptor No. 35-38 were made and evaluated. The results are also shown in Table 5.
Charge transport material no. 2

Examples 39-42
In Examples 31-34, the charge transport material No. 1 is a charge transport material No. 1 below. Except for the change to 3 in the same manner as in Example 31, the electrophotographic photoreceptor No. 39-42 were prepared and evaluated. The results are also shown in Table 6.
Charge transport material no. 3 Chemical structural formula

Examples 43-46
In Examples 31-34, the charge transport material No. 1 is a charge transport material No. 1 below. Except for the change to 4, electrophotographic photoreceptors 43 to 46 were prepared and evaluated in the same manner as in Example 31. The results are also shown in Table 7.

Examples 47, 48
Electrophotographic photosensitive members 47 and 48 were prepared and evaluated in the same manner except that the charge generation layer coating solution and the charge transport layer coating solution in Example 16 were changed to the following. The results are also shown in Table 8.

<Synthesis of oxotitanium phthalocyanine>
In the same manner as in Synthesis Example 4 described in JP-A No. 2001-019871, 29.2 g of 1,3-diiminoisoindoline and 200 ml of sulfolane are mixed, and 20.4 g of titanium tetrabutoxide is added dropwise under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised to 180 ° C., and the reaction was carried out by stirring for 5 hours while maintaining the reaction temperature between 170 ° C. and 180 ° C. After completion of the reaction, the mixture was allowed to cool, and then the precipitate was filtered, washed with chloroform until the powder turned blue, then washed several times with methanol, further washed several times with hot water at 80 ° C., and dried. Crude titanyl phthalocyanine was obtained. Dissolve the crude titanyl phthalocyanine in 20 times the amount of concentrated sulfuric acid, add dropwise to 100 times the amount of ice water with stirring, filter the precipitated crystals, and then repeat washing with water until the washing solution becomes neutral, wet cake of titanyl phthalocyanine pigment Got. The X-ray diffraction spectrum of the dried cake is shown in FIG. 2 g of the obtained wet cake was added to 20 g of carbon disulfide and stirred for 4 hours. 100 g of methanol was added to this and stirred for 1 hour, followed by filtration and drying to obtain oxotitanium phthalocyanine crystal powder.

Charge generation layer coating solution Oxotitanium phthalocyanine having powder XD spectrum shown in FIG. 16: 8 parts Polyvinyl butyral (BX-1): 5 parts 2-butanone: 400 parts ◎ Charge transport layer coating liquid / polycarbonate resin (Z Polycarbonate): 10 parts naphthalene tetracarboxylic acid diimide derivative Exemplified Compound No. 4: 1 part of charge transport material No. 1: 7 copies

・トルエン：７０部

-Toluene: 70 parts

(Example 49)
A photosensitive layer coating solution having the following composition was applied on an aluminum cylinder having a diameter of 100 mm and dried to form a 30 μm single layer photosensitive layer to obtain an electrophotographic photosensitive member. (Photoreceptor No. 49)
[Coating solution for photosensitive layer]
X-type metal-free phthalocyanine (FastogenBlue 8120B: manufactured by Dainippon Ink & Chemicals) 2 parts Charge transport material No. 1 represented by the following structural formula 2: 30 copies

ナフタレンテトラカルボン酸ジイミド誘導体Ｎｏ．７： ２０部
ビスフェノールＺポリカーボネート（パンライトＴＳ−２０５０、帝人化成製）： ５０部
テトラヒドロフラン： ５００部

Naphthalene tetracarboxylic acid diimide derivative no. 7: 20 parts Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals): 50 parts Tetrahydrofuran: 500 parts

The produced electrophotographic photosensitive member is positively charged with a remodeled imagio Neo 752 made by Ricoh using a corona charging method (scorotron type) as a charging method and a semiconductor laser (LD) having an image exposure light source of 780 nm. After setting to (V), a repeated test equivalent to printing a total of 100,000 sheets was continuously performed. At that time, the initial image and the image after the repeated test were evaluated. Further, the bright part potential after the initial and repeated tests was also measured. Further, image blur (dot resolution) was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 9.

(Examples 50 to 52)
Naphthalene tetracarboxylic acid diimide derivative No. The electrophotographic photoreceptor of the present invention was prepared and evaluated in the same manner except that 7 was replaced with that shown in Table 9.

(Example 53)
The same photosensitive layer coating solution as in Example 49 was applied onto an aluminum cylinder with a diameter of 30 mm and dried to form a 30 μm single-layer photosensitive layer to obtain an electrophotographic photosensitive member (photosensitive member No. 53). ).

  Further, the photoreceptor was evaluated in the same manner as in Example 16. The results are shown in Table 10.

(Examples 54 to 56)
Naphthalene tetracarboxylic acid diimide derivative No. 5 of Example 53 The electrophotographic photoreceptor of the present invention was prepared and evaluated in the same manner except that 7 was replaced with that shown in Table 10.

(Example 57)
A 20 μm charge transport layer and a 0.1 μm charge generation layer are formed on a 100 mm diameter aluminum cylinder by sequentially applying and drying a charge transport layer coating solution and a charge generation layer coating solution having the following composition. Then, an electrophotographic photosensitive member was produced (photosensitive member No. 57) and evaluated in the same manner as in Example 53. The evaluation results are shown in Table 11.

[Composition of coating solution for charge transport layer]
Bisphenol A polycarbonate (Panlite C-1400, manufactured by Teijin Chemicals) ... 10 partsToluene ... 100 partsNaphthalene tetracarboxylic acid diimide derivative No. 7:10 parts [Composition of coating solution for charge generation layer]
・ Polyvinyl butyral (XYHL, manufactured by UCC): 0.5 parts ・ Cyclohexanone: 200 parts ・ Methyl ethyl ketone: 80 parts ・ X-type metal-free phthalocyanine (FastogenBlue 8120B: manufactured by Dainippon Ink and Chemicals) 2 parts

(Examples 58 to 60)
Naphthalenetetracarboxylic acid diimide derivative No. 5 of Example 57 The electrophotographic photoreceptor of the present invention was prepared and evaluated in the same manner except that 7 was replaced with that shown in Table 11.

Comparative Example 1
In Example 1, naphthalenetetracarboxylic acid diimide derivative No. Comparative electrophotographic photoreceptor No. 4 was the same as Example 1 except that 4 was changed to the following benzoquinone derivative. 1 was made and evaluated. The results are shown in Table 12.

Comparative Example 2
In Example 16, a comparative electrophotographic photosensitive film was prepared in the same manner as in Example 16 except that the naphthalenetetracarboxylic acid diimide derivative was not added to the charge transport layer forming coating solution and the weight of the charge transport material was 10 parts. Body No. 2 was prepared and evaluated. The results are shown in Table 12.

Comparative Example 3
In Example 35, the same procedure as in Example 35 was repeated except that the naphthalenetetracarboxylic acid diimide derivative was changed to the following tetraphenylmethane compound (described in JP-A No. 2000-231204). 3 was made and evaluated. The results are shown in Table 12.

Comparative Example 4
In Example 47, except that the naphthalene tetracarboxylic acid diimide derivative was changed to the following hindered amine antioxidant, the same procedure as in Example 47 was carried out. 4 was prepared and evaluated. The results are shown in Table 12.

Comparative Example 5
In Example 49, naphthalenetetracarboxylic acid diimide derivative no. Comparative electrophotographic photosensitive member No. 7 was prepared in the same manner as in Example 49 except that 7 and 20 parts were changed to the following electron transport materials. 5 was prepared and evaluated in the same manner. The results are shown in Table 12.

18 parts of charge transport material represented by the following structural formula

下記構造式で表わされる電荷輸送物質 ２部

2 parts of charge transport material represented by the following structural formula

Comparative Example 6
In Example 57, naphthalenetetracarboxylic acid diimide derivative No. Comparative electrophotographic photosensitive member No. 7 was prepared in the same manner as in Example 57 except that 7 and 10 parts were changed to the following electron transport materials. 6 was prepared and evaluated in the same manner. The results are shown in Table 12.
9 parts of charge transport material represented by the following structural formula

下記構造式で表わされる電荷輸送物質 １部

1 part of charge transport material represented by the following structural formula

  From the above evaluation results, it was confirmed that the bright portion potential increase was small even after printing 100,000 sheets, and that the photoconductor containing the naphthalene tetracarboxylic acid diimide derivative of the present invention can stably obtain a high quality image. On the other hand, the comparative photoconductors 1, 3 and 4 have a very high bright portion potential from the beginning, causing a decrease in image density and a decrease in resolution, and the gradation is significantly decreased after printing 100,000 sheets. Image discrimination was impossible. Further, from the evaluation results of Tables 1 and 9, the photoreceptor of the present invention can obtain a good image even in the positive charging system, and the image quality is good even after printing 100,000 sheets, and the image blur (dot resolution) evaluation result. Was also good. Moreover, although the comparative photoconductors 2, 5, and 6 have a relatively small increase in the bright portion potential, the resolution decrease due to repeated use is large compared to the photoconductor of the present invention.

Examples 61-67, Comparative Example 7
Further, the electrophotographic photoreceptor of the present invention and the comparative photoreceptor 2 were left in a desiccator adjusted to a nitrogen oxide (NOx) gas concentration of 50 ppm for 4 days, and image evaluation was performed before and after.

  From the evaluation results in Table 13, it can be seen that the resistance to oxidizing gas, that is, the suppression of reduction in resolution, is greatly improved by including the naphthalene tetracarboxylic acid diimide derivative of the present invention in the photoreceptor. On the other hand, the comparative photoconductor 2 has good initial image quality, but it can be seen that the resolution is significantly reduced by the oxidizing gas.

1 is a cross-sectional view illustrating an electrophotographic photosensitive member of the present invention. 1 is a cross-sectional view illustrating an electrophotographic photosensitive member of the present invention. 1 is a cross-sectional view illustrating an electrophotographic photosensitive member of the present invention. 1 is a cross-sectional view illustrating an electrophotographic photosensitive member of the present invention. 1 is a cross-sectional view illustrating an electrophotographic photosensitive member of the present invention. 1 is a cross-sectional view illustrating an electrophotographic photosensitive member of the present invention. It is the schematic for demonstrating the electrophotographic process and electrophotographic apparatus of this invention. 3 is another example of an electrophotographic process according to the present invention. FIG. 3 is a schematic view for explaining an electrophotographic process cartridge according to the present invention. It is an infrared absorption spectrum (KBr tablet method) of compound No20. It is an infrared absorption spectrum (KBr tablet method) of compound No1. It is an infrared absorption spectrum (KBr tablet method) of compound No10. It is an infrared absorption spectrum (KBr tablet method) of compound No15. It is an infrared absorption spectrum (KBr tablet method) of compound No37. It is an infrared absorption spectrum (KBr tablet method) of compound No38. It is a figure showing the powder XD spectrum of oxotitanium phthalocyanine.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Charger before transfer 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation nail 13 Charger before cleaning 14 Fur brush 15 Cleaning blade 16 Photoconductor 17 Charging Charger 18 Cleaning Brush 19 Image Exposure Unit 20 Developing Roller 21 Photoconductor 22a Drive Roller 22b Drive Roller 23 Charger Charger 24 Image Exposure Source 25 Transfer Charger 26 Pre-Cleaning Exposure 27 Cleaning Brush 28 Static Electricity Light Source 31 Conductive Support 33 Photosensitive Layer 35 charge generation layer 37 charge transport layer 39 protective layer

Claims (14)

An electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains a naphthalene tetracarboxylic acid diimide derivative represented by the following general formula (1). An electrophotographic photosensitive member.

[Wherein R ¹ , R ² , R ³ , R ⁴ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, R ⁵ , R ⁶ , R ⁷ , R ⁸ are A hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group may be the same or different. However, R ¹ and R ² are not bonded to each other. R ³ and R ⁴ are not bonded to each other . ]   2. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is formed by sequentially laminating at least a charge generation layer and a charge transport layer.   2. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is formed by sequentially laminating at least a charge transport layer and a charge generation layer.   2. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is a single-layer type photosensitive layer.   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer further contains a charge transport material. 6. The electrophotographic photoreceptor according to claim 5, wherein the charge transport material is a stilbene derivative represented by the following general formula (2).

[Wherein, X represents a single bond or a vinylene group, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ represents a substituted or unsubstituted aromatic group. Represents a hydrocarbon group, R ⁵ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ and R ⁵ may form a ring together. A represents General formula (3), General formula (4), 9-anthryl group, or a substituted or unsubstituted carbazolyl group.

Here, R ² represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or general formula (5), m represents an integer of 1 to 3, and when 2 or more, R ² may be the same or different.

(However, R ³ and R ⁴ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and R ³ and R ⁴ may be the same or different and may form a ring. good). ] 6. The electrophotographic photoreceptor according to claim 5, wherein the charge transport material is an aminobiphenyl derivative represented by the following general formula (6).

[Wherein R ¹ , R ³ and R ⁴ are a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom or a substituted or unsubstituted group. R ² represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group or a halogen atom. K, l, m and n are integers of ¹ , ² , 3 or 4, and when each is an integer of 2, 3 or 4, R ¹ , R ² , R ³ and R ⁴ may be the same. It may be different. ] 6. The electrophotographic photoreceptor according to claim 5, wherein the charge transport material is a distilbene derivative represented by the following general formula (7).

[Wherein, X represents a single bond or a vinylene group, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ represents a substituted or unsubstituted aromatic group. Represents a hydrocarbon group, R ³ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ and R ³ may form a ring together. R ⁴ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. Ar ² represents the following general formula (8) or general formula (9).

Here, R ² represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 1 to 3, and R ² may be the same or different when 2 or more. ] 6. The electrophotographic photosensitive member according to claim 5, wherein the charge transport material is a divinyl derivative represented by the following general formula (10).

[Wherein, X represents a single bond or a vinylene group, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and Ar ¹ represents a substituted or unsubstituted 2 group. R ⁵ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and A represents a general formula (3), a general formula (4), 9 -Represents an anthryl group or a substituted or unsubstituted carbazolyl group.

Here, R ² represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or general formula (5). m represents an integer of 1 to 3, and when 2 or more, R ² may be the same or different.

(However, R ³ and R ⁴ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, and R ³ and R ⁴ may be the same or different and may form a ring. good). ]   An electrophotographic method in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. Electrophotographic method.   Digital electrophotography in which at least charging, image exposure, development, and transfer are repeated on an electrophotographic photosensitive member, and an electrostatic latent image is written on the photosensitive member by an LD or LED during image exposure. 10. An electrophotographic method, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1.   An electrophotographic apparatus comprising at least a charging unit, an image exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. An electrophotographic apparatus characterized by the above.   An electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein an electrostatic latent image is formed on the photosensitive member by using an LD or an LED as the image exposing unit. An electrophotographic apparatus according to claim 1, wherein the electrophotographic photosensitive body is an electrophotographic photosensitive body according to claim 1, wherein an image is written.   10. A process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. .

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